JP2009079200A - Prepreg, laminate, and metal foil-clad laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a prepreg sufficiently reduced in dust generation in processing, which enables formation of a printed wiring board or multilayered wiring board having sufficient adhesion between an insulating layer and a conductive layer, heat resistance and heat impact resistance, and a laminate and a metal foil-clad laminate using the prepreg. <P>SOLUTION: The prepreg comprises a fiber base and a resin composition impregnated in the fiber base. The resin composition includes an epoxy resin having two or more glycidyl groups and a polyamide-imide resin having a weight average molecular weight of 70,000 to 120,000, and the content of the polyamide-imide resin in the resin composition is 1-50 pts.mass to 100 pts.mass of the epoxy resin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a prepreg, a laminate, and a metal foil-clad laminate.

  A laminated board for a printed wiring board can be obtained by stacking a predetermined number of prepregs having an electrically insulating resin composition as a matrix, and integrating them by heating and pressing. In the production of a printed wiring board, when a printed circuit is formed by a subtractive method, a metal-clad laminate is used. This metal-clad laminate is manufactured by stacking a metal foil such as a copper foil on the surface (one side or both sides) of the prepreg and heating and pressing. As the electrically insulating resin, thermosetting resins such as phenol resin, epoxy resin, polyimide resin, bismaleimide-triazine resin and the like are widely used. In addition, a thermoplastic resin such as a fluororesin or a polyphenylene ether resin may be used.

  A prepreg mainly composed of a phenol resin or an epoxy resin is widely used as a material for a metal-clad laminate because the material is inexpensive. In particular, prepregs mainly composed of epoxy resins have been continuously improved, and high heat resistance, halogen-free flame retardancy, low dielectric constant, low dielectric loss, and the like are progressing. However, since these materials are resin systems with a relatively low molecular weight, if processing such as cutting is performed on the B-stage prepreg, resin powder is likely to be generated, and it is necessary to pay attention to contamination of the laminated copper foil due to dust generation. was there.

  On the other hand, with the widespread use of information terminal devices such as personal computers and mobile phones, printed wiring boards mounted on them are becoming smaller and higher in density. Further, the mounting form has progressed from a pin insertion type to a surface mounting type, and further to an area array type represented by BGA (ball grid array) using a plastic substrate. In a substrate on which a bare chip such as a BGA is directly mounted, the connection between the chip and the substrate is generally performed by wire bonding by thermosonic bonding. For this reason, the substrate on which the bare chip is mounted is exposed to a high temperature of 150 ° C. or higher, and the electrically insulating resin needs a certain degree of heat resistance.

  Further, in the above-described substrate, there is a case where so-called repairability is required in which a chip once mounted is removed. In this case, the substrate is heated to the same degree as that during chip mounting, and then chip mounting is performed again, so that heat treatment is further performed. Therefore, a substrate requiring repairability is required to have cyclic thermal shock resistance at high temperatures.

In order to improve the strength of the insulating layer, there is a method using a fiber base with a copper foil in which a copper foil and a sheet-like fiber base with a basis weight of 30 g / m ² or less are bonded via a thermosetting resin of a B stage. It has been proposed (see, for example, Patent Document 1). However, such a fiber base material with a copper foil has not been studied for dust generation.

  In addition, as the processing speed increases, the number of MPU I / Os increases, and the number of terminals connected by wire bonding increases and the terminal width narrows. For this reason, bonding strength between the core substrate and the metal foil on which the circuit is formed is desired to be higher than before, and it is also necessary to refine the roughened shape on the surface of the metal foil in order to produce thinner wiring. Has been. On the other hand, it is considered that surface smoothness is required for circuit conductors as the frequency of signals increases. Magnetic field lines are generated in the vicinity of the current in the conductor, but since the interference of the magnetic field lines is greater at the center of the conductor, the current is concentrated at the periphery and corners. This is called the skin effect, and this tendency increases as the frequency increases. It is thought that the smoother the surface of the conductor, the more the resistance increase due to the skin effect can be suppressed, but the conventional adhesion by the electrically insulating resin is mainly due to the anchor effect on the rough surface of the conductive layer, and the signal has a higher frequency. Are contradictory.

JP 2003-191377 A

  The present invention has been made in view of the above-mentioned problems of the prior art, and forms a printed wiring board or a multilayer wiring board having sufficient adhesion, heat resistance, and thermal shock resistance between an insulating layer and a conductive layer. It is an object of the present invention to provide a prepreg capable of sufficiently generating dust during processing, a laminate using the prepreg, and a metal foil-clad laminate.

  In order to achieve the above object, the present invention comprises a fiber base material and a resin composition impregnated in the fiber base material, the resin composition having an epoxy resin having two or more glycidyl groups, and a weight average And a polyamideimide resin having a molecular weight of 70,000 or more and 120,000 or less, and the content of the polyamideimide resin in the resin composition is 1 to 50 parts by mass with respect to 100 parts by mass of the epoxy resin.

  According to the prepreg of the present invention, a printed wiring board or multilayer wiring board that can sufficiently reduce dust generation during processing and has sufficient adhesion, heat resistance, and thermal shock resistance between the insulating layer and the conductive layer. Can be formed. Further, according to the prepreg of the present invention, since it is excellent in heat resistance and thermal shock resistance, it is possible to form a printed wiring board or multilayer wiring board excellent in solder heat resistance, reflow resistance and crack resistance. . Such an effect is that the resin composition having the above-described structure is less likely to generate resin powder even when subjected to processing such as cutting in a state before curing, and after curing, a conductive layer such as a metal foil and the like The present inventors consider that it can be obtained by bonding the fiber base material with sufficient strength and becoming an insulating material excellent in heat resistance and thermal shock resistance. If the weight average molecular weight of the polyamideimide resin is less than 70,000, it will be difficult to obtain sufficient dust generation prevention and crack resistance, and if it exceeds 120,000, the impregnation property to the fiber substrate and the moldability of the prepreg will be reduced. It becomes insufficient. Further, if the content of the polyamideimide resin is less than 1 part by mass with respect to 100 parts by mass of the epoxy resin, it becomes difficult to prevent dust generation when cutting the prepreg, and the heat resistance is insufficient. Become. On the other hand, when the amount exceeds 50 parts by mass, the impregnation property of the resin composition into the fiber base material is deteriorated, and defects such as voids are generated in the prepreg. When such a prepreg is used as a laminate, the laminate is laminated. The heat resistance of the plate cannot be obtained sufficiently.

  In the prepreg of the present invention, the polyamideimide resin is preferably a siloxane-modified polyamideimide from the viewpoint of high adhesion and high heat resistance.

  The polyamideimide resin is a siloxane-modified polyamideimide obtained by reacting a diimide dicarboxylic acid component containing a reaction product obtained by reacting siloxane diamine and trimellitic anhydride with an aromatic diisocyanate component. Preferably there is.

  Furthermore, from the viewpoint of improving heat resistance and flame retardancy, the polyamideimide resin contains a reaction product obtained by reacting a mixture of a diamine having an aromatic ring and a siloxane diamine with trimellitic anhydride. A siloxane-modified polyamideimide obtained by reacting an acid component with an aromatic diisocyanate component is preferred.

  Moreover, in the prepreg of the present invention, the polyamideimide resin is obtained by reacting a mixture of a diamine having 3 or more aromatic rings and a siloxane diamine, or a siloxane diamine with trimellitic anhydride. A diimide dicarboxylic acid component containing a diimide dicarboxylic acid represented by (1) and a diimide dicarboxylic acid component represented by the following general formula (2), or a diimide dicarboxylic acid component comprising a diimide dicarboxylic acid represented by the following general formula (2); A siloxane-modified polyamideimide obtained by reacting an aromatic diisocyanate component represented by the following general formula (3) is preferable.

［式（１）中、Ｒ^１は、下記一般式（１−１）で表わされる２価の有機基を示す。

[In formula (1), R ¹ represents a divalent organic group represented by the following general formula (1-1).

｛式（１−１）中、Ｘは、

{In Formula (1-1), X is

｝］

}]

［式（２）中、Ｒ^２は、下記一般式（２−１）で表わされる２価の有機基を示す。

[In formula (2), R ² represents a divalent organic group represented by the following general formula (2-1).

｛式（２−１）中、Ｒ^３及びＲ^４は、２価の有機基を示し、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８はそれぞれ独立に、アルキル基、又は置換若しくは無置換のフェニル基を示し、ｎは、１〜５０の整数を示す。｝］

{In Formula (2-1), R ³ and R ⁴ represent a divalent organic group, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group or a substituted or unsubstituted phenyl group. Represents a group, and n represents an integer of 1 to 50. }]

［式（３）中、Ｒ^９は、

[In Formula (3), R ⁹ is

］

]

  Furthermore, from the viewpoint of improving high heat resistance and flame retardancy, the siloxane-modified polyamideimide has a mixing ratio of diamine (a) having 3 or more aromatic rings and siloxane diamine (b) of a / b = 99. .9 / 0.1-0 / 100 molar ratio of diamine component and trimellitic anhydride [total number of moles of component (a) and component (b)] / [number of moles of trimellitic anhydride] = Diimide dicarboxylic acid represented by the above general formula (1) and diimide dicarboxylic acid represented by the above general formula (2) obtained by reacting at a molar ratio of 1.0 / 2.0 to 1.0 / 2.2 A diimide dicarboxylic acid component containing an acid, or a diimide dicarboxylic acid component containing a diimide dicarboxylic acid represented by the above general formula (2) and an aromatic diisocyanate component represented by the above general formula (3) [component (a) as well as( ) The total number of moles of components] / [number of moles of aromatic diisocyanate component] = a siloxane-modified polyamideimide obtained by reacting at a molar ratio of 1.0 / 1.0 to 1.0 / 1.5. preferable.

  Moreover, this invention provides the laminated board formed by heating and pressing a predetermined number of the prepregs of this invention. According to this laminated board, since the dust generation at the time of processing is sufficiently small, it is possible to satisfactorily laminate the copper foil on which circuit formation is performed on the laminated board which is an insulating layer. And since the cured resin composition can exhibit excellent adhesion, heat resistance, and thermal shock resistance, adhesion between the insulating layer and the conductive layer, heat resistance, thermal shock resistance, solder heat resistance, It is possible to form a printed wiring board or a multilayer wiring board having sufficient reflow resistance and crack resistance.

  The present invention also provides a metal foil-clad laminate comprising a substrate obtained by heating and pressing a predetermined number of the prepregs of the present invention, and a metal foil provided on one or both sides of the substrate.

  According to the present invention, it is possible to form a printed wiring board or a multilayer wiring board having sufficient adhesion, heat resistance, and thermal shock resistance between an insulating layer and a conductive layer, and a prepreg with sufficiently low dust generation during processing. In addition, a laminate and a metal foil-clad laminate using the same can be provided.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant descriptions are omitted.

  FIG. 1 is a perspective view showing an embodiment of a prepreg according to the present invention. A prepreg 100 shown in FIG. 1 is a sheet-like prepreg composed of a fiber base material and a resin composition impregnated therein.

  First, the resin composition according to the present invention will be described.

  The resin composition in the prepreg 100 includes an epoxy resin having two or more glycidyl groups and a polyamideimide resin having a weight average molecular weight of 70000 to 120,000, and the content of the polyamideimide resin in the resin composition However, it is necessary that it is 1-50 mass parts with respect to 100 mass parts of said epoxy resins.

  The epoxy resin having two or more glycidyl groups is not particularly limited, and examples thereof include polyhydric phenols such as bisphenol A, novolac type phenol resins, and orthocresol novolac type phenol resins, or 1,4-butanediol. Polyglycidyl esters, amines, amides or heterocyclics obtained by reacting a polybasic acid such as polyglycidyl ether, phthalic acid, hexahydrophthalic acid and the like with epichlorohydrin obtained by reacting a polyhydric alcohol such as polychlorohydrin Examples thereof include N-glycidyl derivatives of compounds having a nitrogen base, alicyclic epoxy resins, and the like. These can be used alone or in combination of two or more.

  The resin composition according to the present invention includes an epoxy resin curing agent having two or more glycidyl groups and an epoxy resin having two or more glycidyl groups in order to improve thermal, mechanical, and electrical characteristics. It is preferable to further contain a curing accelerator or both the curing agent and the curing accelerator.

  The curing agent and curing accelerator for the epoxy resin can be used without limitation as long as they can be cured by reacting with the epoxy resin and can be cured, respectively. For example, amines, imidazoles, polyfunctional phenols, acid anhydrides and the like can be mentioned. Examples of amines include dicyandiamide, diaminodiphenylmethane, and guanylurea. Examples of the polyfunctional phenols include hydroquinone, resorcinol, bisphenol A and their halogen compounds, novolak-type phenol resins that are condensates with formaldehyde, and resole-type phenol resins. Examples of acid anhydrides include phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic acid, and the like. Moreover, as a hardening accelerator, alkyl group substituted imidazole, benzimidazole, etc. can be used as imidazoles.

  The preferred content of the curing agent or curing accelerator in the resin composition according to the present invention is as follows. For example, when an amine is contained, an amount in which the active hydrogen equivalent of the amine and the epoxy equivalent of the epoxy resin are approximately equal is preferable. Moreover, when imidazole which is a hardening accelerator is contained, the content thereof is not simply an equivalent ratio with active hydrogen, and is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin. Moreover, when polyfunctional phenols and acid anhydrides are contained, an amount such that the phenolic hydroxyl group or carboxyl group is 0.6 to 1.2 equivalents relative to 1 equivalent of the epoxy resin is preferable.

  If the content of the curing agent or curing accelerator is less than the above preferred range, an uncured epoxy resin tends to remain, and the Tg (glass transition temperature) of the cured resin tends to be low. On the other hand, when the content of the curing agent and the curing accelerator is more than the above preferable range, unreacted curing agent and curing accelerator are likely to remain, and the insulating property of the resin after curing tends to decrease. . In addition, since an epoxy resin can react with the amide group of a polyamide-imide resin, when setting content of a hardening | curing agent or a hardening accelerator, it is preferable to consider the content of the amide group of a polyamide-imide resin.

  The siloxane-modified polyamideimide resin having a weight average molecular weight of 70,000 to 120,000 is a diimide dicarboxylic acid component containing a reaction product obtained by reacting siloxane diamine with trimellitic anhydride from the viewpoint of reducing the inclusion of ionic impurities. And a siloxane-modified polyamideimide obtained by reacting an aromatic diisocyanate component, or a diimide dicarboxylic acid containing a reaction product obtained by reacting a mixture of a diamine having an aromatic ring and a siloxane diamine with trimellitic anhydride It is preferable to use a siloxane-modified polyamideimide obtained by reacting an acid component with an aromatic diisocyanate component.

  Furthermore, from the viewpoint of improving high heat resistance and flame retardancy, the siloxane-modified polyamideimide contains diimide dicarboxylic acid obtained by reacting a mixture of a diamine having three or more aromatic rings and a siloxane diamine with trimellitic anhydride. More preferably, the mixture is obtained by reacting an aromatic diisocyanate.

  Examples of the diamine having three or more aromatic rings include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter abbreviated as BAPP) and bis [4- (3-aminophenoxy) phenyl] sulfone. Bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] methane, 4 , 4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-amino) Phenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene and the like. These can be used individually by 1 type or in combination of 2 or more types. Among the above diamines, BAPP is more preferable from the viewpoint of the balance of properties of the polyamideimide resin and the cost.

  Examples of the siloxane diamine include those represented by the following general formula (4).

式中Ｒ^１０及びＲ^１１は２価の有機基を示し、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５はそれぞれ独立に、アルキル基、フェニル基又は置換フェニル基を示し、ｍは、１〜１５の整数を示す。

In the formula, R ¹⁰ and R ¹¹ represent a divalent organic group, R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represents an alkyl group, a phenyl group or a substituted phenyl group, and m represents 1 to 15 Indicates an integer.

  As the siloxane diamine represented by the general formula (4), commercially available products can be used. For example, “X-22-161AS” (amine equivalent 450), “X-22-161A” (amine equivalent 840), “X-22-161B” (amine equivalent 1500) (above, trade name manufactured by Shin-Etsu Chemical Co., Ltd.), “BY16-853” (amine equivalent 650), “BY16-853B” (amine equivalent 2200) (above, Toray Industries, Inc.) Amino-modified silicone oils that are dimethylsiloxane-based both-end amines such as Dow Corning Silicone Co., Ltd. trade name).

  Examples of aromatic diisocyanates include 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, and 2,4-tolylene. Dimer etc. are mentioned. These can be used alone or in combination.

  The mixing ratio of the diamine (a) having 3 or more aromatic rings and the siloxane diamine (b) is preferably a / b = 99.9 / 0.1-0 / 100 molar ratio, = 95/5 to 30/70 (molar ratio), more preferably a / b = 90/10 to 40/60 (molar ratio). When the mixing ratio of siloxane diamine (b) increases, Tg tends to decrease, and when it decreases, the amount of varnish solvent remaining in the resin tends to increase when a prepreg is produced.

  Diimide dicarboxylic acid is a mixture of a diamine having 3 or more aromatic rings and a siloxane diamine and trimellitic anhydride, [total number of moles of component (a) and component (b)] / [trimellitic anhydride]. The number of moles of] is preferably obtained by reacting at a molar ratio of 1.0 / 2.0 to 1.0 / 2.2. If the molar ratio is outside this range, and the proportion of trimellitic anhydride decreases, the flexibility of the siloxane-modified polyamideimide resin tends to decrease, while the same tendency occurs even when the proportion of trimellitic anhydride is large. It becomes.

  Furthermore, diimide dicarboxylic acid and aromatic diisocyanate are [[total number of moles of component (a) and component (b)] / [number of moles of aromatic diisocyanate component] = 1.0 / 1.0 to 1.0 / 1. It is preferable to react with a molar ratio of 0.5 to obtain a siloxane-modified polyamideimide. If the molar ratio is outside this range and the proportion of aromatic diisocyanate decreases, it becomes difficult to obtain a siloxane-modified polyamideimide resin having a weight average molecular weight of 70000 or more, and even if the proportion of aromatic diisocyanate is large, the weight average It becomes difficult to obtain a siloxane-modified polyamideimide resin having a molecular weight of 70,000 or more, and the stability of the obtained polyamideimide resin tends to deteriorate.

  In this embodiment, a diimide dicarboxylic acid obtained by reacting a mixture of a diamine having 3 or more aromatic rings and a siloxane diamine with trimellitic anhydride is a diimide dicarboxylic acid represented by the following general formula (1). And what contains the diimide dicarboxylic acid shown by following General formula (2) is preferable. Moreover, what contains diimide dicarboxylic acid shown by following General formula (2) as diimide dicarboxylic acid obtained by making siloxane diamine and trimellitic anhydride react is preferable. As aromatic diisocyanate, what is shown by following General formula (3) is preferable.

［式（１）中、Ｒ^１は、下記一般式（１−１）で表わされる２価の有機基を示す。

[In formula (1), R ¹ represents a divalent organic group represented by the following general formula (1-1).

｛式（１−１）中、Ｘは、

{In Formula (1-1), X is

｝］

}]

［式（２）中、Ｒ^２は、下記一般式（２−１）で表わされる２価の有機基を示す。

[In formula (2), R ² represents a divalent organic group represented by the following general formula (2-1).

｛式（２−１）中、Ｒ^３及びＲ^４は、２価の有機基を示し、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８はそれぞれ独立に、アルキル基、又は置換若しくは無置換のフェニル基を示し、ｎは、１〜５０の整数を示す。｝］

{In Formula (2-1), R ³ and R ⁴ represent a divalent organic group, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group or a substituted or unsubstituted phenyl group. Represents a group, and n represents an integer of 1 to 50. }]

［式（３）中、Ｒ^９は、

[In Formula (3), R ⁹ is

］

]

  In the siloxane-modified polyamideimide, the mixing ratio of the diamine (a) having three or more aromatic rings and the siloxane diamine (b) is a / b = 99.9 / 0.1-0 / 100 molar ratio. The diamine component and trimellitic anhydride are [total number of moles of component (a) and component (b)] / [number of moles of trimellitic anhydride] = 1.0 / 2.0 to 1.0 / 2. The diimide dicarboxylic acid component containing the diimide dicarboxylic acid represented by the general formula (1) and the diimide dicarboxylic acid represented by the general formula (2) obtained by reacting at a molar ratio of .2 or the general formula (2 The diimide dicarboxylic acid component containing the diimide dicarboxylic acid represented by the formula (1) and the aromatic diisocyanate component represented by the general formula (3) above [total number of moles of the components (a) and (b)] / [aromatic Diiso It is preferably a siloxane-modified polyamideimide obtained by reacting in a molar ratio of Aneto moles of component] = 1.0 / 1.0 to 1.0 / 1.5.

  Furthermore, the mixing ratio of the diamine (a) having 3 or more aromatic rings and the siloxane diamine (b) is more preferably a / b = 95/5 to 30/70 (molar ratio), and a / b = Even more preferably 90/10 to 40/60 (molar ratio). When the mixing ratio of siloxane diamine (b) increases, Tg tends to decrease, and when it decreases, the amount of varnish solvent remaining in the resin tends to increase when a prepreg is produced.

  The molar ratio of diamine to trimellitic anhydride [total number of moles of component (a) and component (b)] / [number of moles of trimellitic anhydride] is preferably 1.0 / 2 as described above. 0.0 to 1.0 / 2.2. If the molar ratio is outside this range, and the proportion of trimellitic anhydride decreases, the flexibility of the siloxane-modified polyamideimide resin tends to decrease, while the same tendency occurs even when the proportion of trimellitic anhydride is large. It becomes.

  Furthermore, diimide dicarboxylic acid and aromatic diisocyanate are [[total number of moles of component (a) and component (b)] / [number of moles of aromatic diisocyanate component] = 1.0 / 1.0 to 1.0 / 1. It is preferable to react with a molar ratio of 0.5 to obtain a siloxane-modified polyamideimide. If the molar ratio is outside this range and the proportion of aromatic diisocyanate decreases, it becomes difficult to obtain a siloxane-modified polyamideimide resin having a weight average molecular weight of 70000 or more, and even if the proportion of aromatic diisocyanate is large, the weight average It becomes difficult to obtain a siloxane-modified polyamideimide resin having a molecular weight of 70,000 or more, and the stability of the obtained polyamideimide resin tends to deteriorate.

  The resin composition according to the present invention needs to contain a polyamideimide resin having a weight average molecular weight of 70,000 to 120,000. If the weight average molecular weight of the polyamideimide resin is less than 70,000, it will be difficult to obtain sufficient dust generation prevention and crack resistance, and if it exceeds 120,000, the impregnation property to the fiber substrate and the moldability of the prepreg will be reduced. It becomes insufficient.

  In the present invention, the weight average molecular weight of the polyamideimide resin means a value measured by general gel permeation chromatography. The column used in the measurement is not particularly limited as long as the weight average molecular weight can separate several thousand to 200,000. The eluent is not particularly limited as long as it can dissolve the polyamideimide resin, but a mixed liquid of tetrahydrofuran and dimethylformamide is preferable. In order to prevent the apparent molecular weight from increasing due to the association between the polyamideimide resins, it is preferable to add phosphoric acid and a salt thereof to the mixed solution.

  The content of the polyamideimide resin having a weight average molecular weight of 70000 to 120,000 in the resin composition according to the present invention needs to be 1 to 50 parts by mass with respect to 100 parts by mass of the epoxy resin having two or more glycidyl groups. It is. If the content of the polyamideimide resin is less than 1 part by mass, it will be difficult to prevent dust generation when the prepreg is cut, and the heat resistance will be insufficient. On the other hand, when the content exceeds 50 parts by mass, the impregnation property of the resin composition into the fiber base material is deteriorated, and defects such as voids are generated in the prepreg. When such a prepreg is used as a laminated board Therefore, sufficient heat resistance of the laminated plate cannot be obtained.

  Furthermore, from the viewpoint of dust generation prevention, crack resistance and moldability, the content of the polyamideimide resin having a weight average molecular weight of 70,000 to 120,000 is 5 with respect to 100 parts by mass of the epoxy resin having two or more glycidyl groups. -40 mass parts is more preferable, and 15-30 mass parts is further more preferable.

  The resin composition according to the present invention may contain a flame retardant for the purpose of improving flame retardancy. Examples of the flame retardant include “OP930” (trade name, manufactured by Clariant), “HP-360” (trade name, manufactured by Showa Denko KK), “HCA-HQ” (manufactured by Sanko Co., Ltd.), which are additive-type flame retardants. Product name), melamine polyphosphates “PMP-100”, “PMP-200”, “PMP-300” (the product name manufactured by Nissan Chemical Co., Ltd.) and the like.

  The prepreg 100 is preferably produced by impregnating a fiber base material with a varnish obtained by mixing, dissolving, and dispersing an organic solvent in the resin composition according to the present invention, and drying. The organic solvent is not particularly limited as long as the solubility of the resin composition can be obtained. For example, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methyl-2- Examples include pyrrolidone, γ-butyrolactone, sulfolane, and cyclohexanone.

  The varnish impregnated into the fiber substrate can be dried at, for example, 80 ° C to 180 ° C. Moreover, it is preferable to set drying time suitably according to the gelatinization time of a varnish. Furthermore, it is preferable that 80 mass% or more of the organic solvent contained in the varnish volatilizes. The amount of the varnish impregnated in the resin composition is preferably such that the solid content in the varnish is 35 to 70 mass% with respect to the total amount of the solid content in the varnish and the fiber base material.

  The fiber substrate is not particularly limited as long as it is generally used when producing a metal foil-clad laminate or a multilayer printed wiring board, but a fiber substrate such as a woven fabric or a nonwoven fabric is usually used. Examples of the fiber base material include glass, alumina, asbestos, boron, silica alumina glass, silica glass, tyrano, silicon carbide, silicon nitride, zirconia, and other inorganic fibers, aramid, polyetheretherketone, polyetherimide, polyether Examples thereof include organic fibers such as sulfone, carbon and cellulose, and mixed papers thereof. Among these, a glass fiber woven fabric is particularly preferably used.

  Moreover, it is preferable that the thickness of a fiber base material is 5-100 micrometers. Furthermore, as a fiber base material used for the prepreg, a glass cloth of 5 to 50 μm is particularly preferably used from the viewpoint of bendability.

  A laminate (insulating plate) using the prepreg of the present invention is produced as follows. First, one or a plurality of prepregs of the present invention are laminated to obtain a laminate. Next, the laminate is heated and pressure-molded at a temperature usually in the range of 150 to 280 ° C, preferably in the range of 170 ° C to 240 ° C, and usually in the range of 0.5 to 20 MPa, preferably in the range of 1 to 8 MPa. Thus, a laminated plate (insulating plate) is produced.

  A metal-clad laminate using the prepreg of the present invention is produced as follows. A metal foil is laminated on one side or both sides of the prepreg of the present invention or a laminate obtained by laminating a plurality of the prepregs, usually at a temperature in the range of 150 to 280 ° C., preferably 170 ° C. to 240 ° C. A metal-clad laminate is produced by hot pressing under a pressure in the range of 1 to 8 MPa. Furthermore, a printed circuit board can be obtained by performing circuit processing on the metal foil of the metal-clad laminate.

  FIG. 2 is a partial cross-sectional view showing an embodiment of a metal foil-clad laminate according to the present invention. The metal foil-clad laminate 200 includes a sheet-like substrate 30 obtained by heating and pressing a laminate in which a plurality of prepregs 100 are laminated, and two metal foils 10 provided in close contact with both surfaces of the substrate 30. It consists of.

  The substrate 30 is made of a laminate in which a plurality of fiber reinforced resin layers 3 derived from a plurality of prepregs 100 are laminated. In order to increase the flexibility of the metal foil-clad laminate and the printed circuit board, the thickness of the substrate 30 is preferably 20 to 180 μm. In each fiber reinforced resin layer 3, the fiber base material is impregnated with resin as a matrix. This resin is a cured product of the resin composition according to the present invention described above.

  The metal foil-clad laminate is obtained by stacking metal foil on both sides of a laminate in which a predetermined number (preferably two or less) of prepregs 100 are laminated, and heating and pressing the laminate. At this time, the heating temperature and pressure are not particularly limited, but the heating temperature is usually 150 to 280 ° C. (preferably 170 to 240 ° C.), and the pressure is usually 0.5 to 20 MPa (preferably 1 to 8 MPa). It is.

  As the metal foil 10, a copper foil or an aluminum foil is generally used, but a copper foil is preferable. The metal foil 10 having a thickness of 5 to 200 μm, which is used for a normal metal foil-clad laminate, can be used, but the thickness is 5 to 35 μm in order to increase the flexibility of the printed circuit board. It is more preferable. Also, nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy, etc. are used as intermediate layers, and a 0.5-15 μm copper layer and a 10-300 μm copper layer are provided on both sides. Alternatively, a three-layer composite foil or a two-layer composite foil in which aluminum and copper foil are combined can be used.

  The embodiment of the metal foil-clad laminate is not limited to the above aspect. For example, using one prepreg 100, the substrate may be composed of one fiber reinforced resin layer, or a metal foil may be provided on only one side of the substrate. Moreover, a printed circuit board can be obtained by patterning the metal foil of the metal foil-clad laminate by etching or the like.

  FIG. 3 is a schematic cross-sectional view showing an embodiment of a printed circuit board obtained using the prepreg of the present invention. The printed circuit board 300 shown in FIG. 3 is a multilayer printed circuit board, and includes an inner layer circuit board 315 formed by arranging inner layer circuits 313a and 313b on both sides of an insulating substrate 310 in which a through hole 311 is filled with a conductor 312. Insulating substrates 320a, b provided on both sides of the inner circuit board 315, with through holes 321a, b filled with conductors 322a, b, respectively, and circuits 323a formed outside the insulating substrates 320a, 320b , B.

  The printed circuit board 300 is formed as follows, for example. First, the prepreg 100 according to the present invention is laminated on both sides of the inner layer circuit board 315 and cured by heating and pressurization to form the insulating substrates 320a and 320b. Next, through holes 321a and b are provided in the insulating substrates 320a and 320b, and conductors 322a and b are filled therein. Then, patterned circuits 323a and 323b are formed outside the insulating substrates 320a and 320b to complete the printed circuit board 300.

  Alternatively, the prepreg 100 according to the present invention is laminated on both sides of the inner layer circuit board 315, through holes 321a and b are provided, and conductors 322a and b are filled therein. Further, a metal foil is laminated on the outside of the prepreg 100 and heated and pressurized, and then the metal foil is patterned by etching or the like to form circuits 323a and b, thereby completing the printed circuit board 300.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples.

[Synthesis of Polyamideimide]
(Synthesis Example 1)
BAPP (2,2-bis [4] as a diamine having 3 or more aromatic rings was added to a 1-liter separable flask equipped with a 25 ml moisture meter with a cock connected to a reflux condenser, a thermometer and a stirrer. -(4-aminophenoxy) phenyl] propane) 57.5 g (0.07 mol), reactive silicon oil KF-8010 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 421) as siloxane diamine 50.5 g (0. 03 mol), 80.7 g (0.21 mol) of TMA (trimellitic anhydride), and 460 g of NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent, and the reaction solution at 80 ° C. for 30 minutes Stir. Further, 100 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and then the temperature of the reaction solution was raised and refluxed at about 160 ° C. for 2 hours. While confirming that approximately 7.2 ml or more of water has accumulated in the moisture determination receiver and that no distillation of water has been observed, while removing the distillate accumulated in the moisture determination receiver, The temperature was raised to 0 ° C. to remove toluene. Thereafter, 60.1 g (0.12 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate to the reaction solution returned to room temperature, and reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of siloxane-modified polyamideimide resin was obtained. The weight average molecular weight of the obtained siloxane-modified polyamideimide resin was 82,000 in terms of polystyrene by GPC (gel permeation chromatography).

(Synthesis Example 2)
BAPP (2,2-bis [4] as a diamine having 3 or more aromatic rings was added to a 1-liter separable flask equipped with a 25 ml moisture meter with a cock connected to a reflux condenser, a thermometer and a stirrer. -(4-aminophenoxy) phenyl] propane) 41.1 g (0.05 mol), reactive silicon oil KF-8010 (trade name, amine equivalent 421, manufactured by Shin-Etsu Chemical Co., Ltd.) as a siloxane diamine, 84.2 g (0. 05 mol), 80.7 g (0.21 mol) of TMA (trimellitic anhydride), and 494 g of NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent, and the reaction solution at 80 ° C. for 30 minutes Stir. Further, 100 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and then the temperature of the reaction solution was raised and refluxed at about 160 ° C. for 2 hours. While confirming that approximately 7.2 ml or more of water has accumulated in the moisture determination receiver and that no distillation of water has been observed, while removing the distillate accumulated in the moisture determination receiver, The temperature was raised to 0 ° C. to remove toluene. Thereafter, 60.1 g (0.12 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate to the reaction solution returned to room temperature, and reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of siloxane-modified polyamideimide resin was obtained. The weight average molecular weight of the obtained siloxane-modified polyamideimide resin was 78000 in terms of polystyrene by GPC.

(Synthesis Example 3)
BAPP (2,2-bis [4] as a diamine having 3 or more aromatic rings was added to a 1-liter separable flask equipped with a 25 ml moisture meter with a cock connected to a reflux condenser, a thermometer and a stirrer. -(4-aminophenoxy) phenyl] propane) 16.4 g (0.02 mol), reactive silicon oil KF-8010 (trade name, amine equivalent 421 manufactured by Shin-Etsu Chemical Co., Ltd.) as a siloxane diamine 134.7 g (0. 08 mol), 80.7 g (0.21 mol) of TMA (trimellitic anhydride) and 438 g of NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent, and the reaction solution at 80 ° C. for 30 minutes Stir. Further, 100 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and then the temperature of the reaction solution was raised and refluxed at about 160 ° C. for 2 hours. While confirming that approximately 7.2 ml or more of water has accumulated in the moisture determination receiver and that no distillation of water has been observed, while removing the distillate accumulated in the moisture determination receiver, The temperature was raised to 0 ° C. to remove toluene. Thereafter, 60.1 g (0.12 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate to the reaction solution returned to room temperature, and reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of a siloxane-modified polyamideimide resin was obtained. The weight average molecular weight of the obtained siloxane-modified polyamideimide resin was 76000 in terms of polystyrene by GPC.

(Synthesis Example 4)
BAPP (2,2-bis [4] as a diamine having 3 or more aromatic rings was added to a 1-liter separable flask equipped with a 25 ml moisture meter with a cock connected to a reflux condenser, a thermometer and a stirrer. -(4-aminophenoxy) phenyl] propane) 41.1 g (0.05 mol), reactive silicon oil KF-8010 (trade name, amine equivalent 421, manufactured by Shin-Etsu Chemical Co., Ltd.) as a siloxane diamine, 84.2 g (0. 05 mol), 80.7 g (0.21 mol) of TMA (trimellitic anhydride), and 495 g of NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent, and the reaction solution at 80 ° C. for 30 minutes Stir. Further, 100 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and then the temperature of the reaction solution was raised and refluxed at about 160 ° C. for 2 hours. While confirming that approximately 7.2 ml or more of water has accumulated in the moisture determination receiver and that no distillation of water has been observed, while removing the distillate accumulated in the moisture determination receiver, The temperature was raised to 0 ° C. to remove toluene. Thereafter, 60.1 g (0.12 mol) of MDI (4,4′-diphenylmethane diisocyanate) as an aromatic diisocyanate and 1 ml of triethylamine were added to the reaction solution returned to room temperature, and reacted at 170 ° C. for 4 hours. After completion of the reaction, an NMP solution of a siloxane-modified polyamideimide resin was obtained. The weight average molecular weight of the obtained siloxane-modified polyamideimide resin was 105000 in terms of polystyrene by GPC.

(Synthesis Example 5)
BAPP (2,2-bis [4] as a diamine having 3 or more aromatic rings was added to a 1-liter separable flask equipped with a 25 ml moisture meter with a cock connected to a reflux condenser, a thermometer and a stirrer. -(4-aminophenoxy) phenyl] propane) 8.2 g (0.01 mol), reactive silicone oil KF-8010 (trade name, amine equivalent 421 manufactured by Shin-Etsu Chemical Co., Ltd.) as a siloxane diamine 151.6 g (0. 09 mol), 80.7 g (0.21 mol) of TMA (trimellitic anhydride), and 495 g of NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent, and the reaction solution at 80 ° C. for 30 minutes Stir. Further, 100 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and then the temperature of the reaction solution was raised and refluxed at about 160 ° C. for 2 hours. While confirming that approximately 7.2 ml or more of water has accumulated in the moisture determination receiver and that no distillation of water has been observed, while removing the distillate accumulated in the moisture determination receiver, The temperature was raised to 0 ° C. to remove toluene. Thereafter, 60.1 g (0.12 mol) of MDI (4,4′-diphenylmethane diisocyanate) as an aromatic diisocyanate and 1 ml of triethylamine were added to the reaction solution returned to room temperature, and reacted at 170 ° C. for 4 hours. After completion of the reaction, an NMP solution of siloxane-modified polyamideimide resin was obtained. The weight average molecular weight of the obtained siloxane-modified polyamideimide resin was 76000 in terms of polystyrene by GPC.

(Comparative Synthesis Example 1)
BAPP (2,2-bis [4] as a diamine having 3 or more aromatic rings was added to a 1-liter separable flask equipped with a 25 ml moisture meter with a cock connected to a reflux condenser, a thermometer and a stirrer. -(4-aminophenoxy) phenyl] propane) 41.1 g (0.05 mol), reactive silicon oil KF-8010 (trade name, amine equivalent 421, manufactured by Shin-Etsu Chemical Co., Ltd.) as a siloxane diamine, 84.2 g (0. 05 mol), 80.7 g (0.21 mol) of TMA (trimellitic anhydride), and 346 g of NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent, and the reaction solution at 80 ° C. for 30 minutes Stir. Further, 100 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and then the temperature of the reaction solution was raised and refluxed at about 160 ° C. for 2 hours. While confirming that approximately 7.2 ml or more of water has accumulated in the moisture determination receiver and that no distillation of water has been observed, while removing the distillate accumulated in the moisture determination receiver, The temperature was raised to 0 ° C. to remove toluene. Thereafter, 60.1 g (0.12 mol) of MDI (4,4′-diphenylmethane diisocyanate) as an aromatic diisocyanate and 1.5 ml of triethylamine were added to the reaction solution returned to room temperature, and reacted at 160 ° C. for 5 hours. . After completion of the reaction, an NMP solution of siloxane-modified polyamideimide resin was obtained. The weight average molecular weight of the obtained siloxane-modified polyamideimide resin was 129000 in terms of polystyrene by GPC.

(Comparative Synthesis Example 2)
BAPP (2,2-bis [4] as a diamine having 3 or more aromatic rings was added to a 1-liter separable flask equipped with a 25 ml moisture meter with a cock connected to a reflux condenser, a thermometer and a stirrer. -(4-aminophenoxy) phenyl] propane) 41.1 g (0.05 mol), reactive silicon oil KF-8010 (trade name, amine equivalent 421, manufactured by Shin-Etsu Chemical Co., Ltd.) as a siloxane diamine, 84.2 g (0. 05 mol), 80.7 g (0.21 mol) of TMA (trimellitic anhydride), and 494 g of NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent, and the reaction solution at 80 ° C. for 30 minutes Stir. Further, 100 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and then the temperature of the reaction solution was raised and refluxed at about 160 ° C. for 2 hours. While confirming that approximately 7.2 ml or more of water has accumulated in the moisture determination receiver and that no distillation of water has been observed, while removing the distillate accumulated in the moisture determination receiver, The temperature was raised to 0 ° C. to remove toluene. Thereafter, 52.6 g (0.105 mol) of MDI (4,4′-diphenylmethane diisocyanate) as an aromatic diisocyanate was added to the reaction solution returned to room temperature, and reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of siloxane-modified polyamideimide resin was obtained. The weight average molecular weight of the obtained siloxane-modified polyamideimide resin was 45000 in terms of polystyrene by GPC.

The weight average molecular weights of the siloxane-modified polyamideimide resins obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 and 2 were measured by gel permeation chromatography (GPC) under the following conditions. It is a value converted using a calibration curve.
(GPC conditions)
Detector: L-7490 (manufactured by Hitachi, Ltd.)
Column: GL-S300MDT-5 (2) (Hitachi Chemical Industry Co., Ltd. trade name)
Eluent: DMF / THF mixture containing 0.60 M H ₃ PO ₄ and 0.30 M LiBr (volume ratio: DMF / THF = 1/1)
Measurement temperature: 30 ° C
Sample concentration: 0.2 mg / 1 mL
Injection volume: 100 μL
Pressure: 4MPa
Flow rate: 1 mL / min

Example 1
<Preparation of resin composition varnish>
First, 300 g of YDCN-702 (trade name manufactured by Toto Kasei Co., Ltd., epoxy equivalent 210), 400 g of EPICLON 860 (trade name manufactured by Dainippon Ink Co., Ltd., epoxy equivalent 240) and NC3000 (trade name manufactured by Nippon Kayaku Co., Ltd.) are used as epoxy resins. , Epoxy equivalent 289) 300 g, and 496 g of KA-1165 (trade name, hydroxyl equivalent 120) manufactured as a phenol resin in a mixed solvent of 900 g of methyl ethyl ketone and 100 g of dimethylacetamide, and then used as a flame retardant is aluminum hydroxide. 300 g of HP-360 (trade name, manufactured by Showa Denko KK) was dispersed, 10 g of 2E4MZ-CN was further added as a curing accelerator, and the mixture was stirred for 1 hour. Next, an NMP solution (resin of the siloxane-modified polyamideimide resin of Synthesis Example 1 is added to this mixture so that the amount of the siloxane-modified polyamideimide resin is 20 parts by mass with respect to 100 parts by mass of the total epoxy resin. After mixing for about 1 hour until the resin became homogeneous, the mixture was allowed to stand at room temperature for 12 hours for defoaming to obtain a resin composition varnish.

<Preparation of prepreg>
The resin composition varnish prepared above was impregnated into a glass cloth having a thickness of about 0.1 mm (manufactured by Nitto Boseki Co., Ltd., trade name “GA-7010”, E-glass), and then heated at 150 ° C. for 15 minutes. And dried to obtain a prepreg having a resin content of 45% by mass.

<Production of double-sided copper-clad laminate>
Four prepregs produced in the same manner as described above are laminated to form a laminate, and a copper foil having a thickness of 18 μm (Furukawa Metal Co., Ltd., trade name “F3-WS-18” or “F0-WS” is formed on both sides of the laminate. −18 ”) is laminated so that the adhesive surface is aligned with the prepreg, and heated and pressurized under the press conditions of 180 ° C., 90 minutes, 4.0 MPa, and two types of the double-sided copper-clad laminate of Example 1 (as copper foil) "F3-WS-18" and "F0-WS-18") were obtained.

<Evaluation items for prepreg and double-sided copper-clad laminate>
(1) Dust generation property of prepreg Ten obtained prepregs were cut into a size of width 1 cm × length 25 cm with a cutter (manufactured by Olfa), and the dust generation property was evaluated by the presence or absence of resin powder generated at this time. . The results are shown in Table 1. In addition, about the result, the case where resin powder was seen was shown as "with dust generation", and the case where resin powder was not seen was shown as "without dust generation".

(2) Solder heat resistance The obtained double-sided copper-clad laminate (copper foil: “F3-WS-18” manufactured by Furukawa Metal Co., Ltd.) was immersed in each of the solder baths heated to 260 ° C. and 288 ° C. The state of the laminate 20 seconds after the start was visually observed, and the solder heat resistance was evaluated by the presence or absence of abnormalities such as blistering. The results are shown in Table 1. As for the results, a case where no abnormality such as blistering was observed was indicated by “◯”, and a case where abnormality such as blistering was observed was indicated by “x”.

(3) Copper foil peeling strength (copper foil adhesive strength)
The obtained double-sided copper-clad laminate was subjected to a 90 ° peel test, and the strength at that time was defined as the copper foil peel strength (copper foil adhesive strength). The results are shown in Table 1. The copper foil peel strength when the copper foil is “F3-WS-18” is defined as copper foil adhesive strength 1, and the copper foil peel strength when “F0-WS-18” is defined as the copper foil adhesive strength. It is shown in the table as 2.

(4) Impact resistance On the obtained double-sided copper-clad laminate, four rows of daisy chain patterns having 250 connection holes with a diameter of 0.25 mm were prepared by ordinary drilling, plating, and photolithographic processes. The end points were connected by lead wires with solder, each printed circuit board having a conduction pattern of 1000 holes in a row was produced, and the initial resistance of the conduction pattern was measured. Thereafter, each printed circuit board was mounted on a predetermined housing, dropped a predetermined number of times from a height of 1.5 m, and the resistance value after dropping was measured. The impact resistance was evaluated by the rate of change in resistance from the initial resistance value after dropping 1000 times, the presence or absence of disconnection, and the presence or absence of cracks in the resin part. The results are shown in Table 2.

(5) Thermal shock resistance On the obtained double-sided copper-clad laminate, four rows of daisy chain patterns having 250 connection holes with a diameter of 0.25 mm were prepared by ordinary drilling, plating, and photolithography processes. The end points were connected by lead wires with solder, each printed circuit board having a conduction pattern of 1000 holes in a row was produced, and the initial resistance of the conduction pattern was measured. After that, for each printed circuit board, a thermal shock tester (manufactured by ETAC, “TC100”) was used, and a thermal cycle with 125 cycles of 30 ° C./−65° C. for 30 minutes was performed 1000 cycles, and after 1000 cycles The resistance value of was measured. Thermal shock resistance was evaluated based on the rate of change in resistance from the initial resistance value after 1000 cycles, the presence or absence of disconnection, and the presence or absence of cracks in the resin part. The results are shown in Table 2.

(Example 2)
Instead of the siloxane-modified polyamideimide resin solution of Synthesis Example 1, the siloxane-modified polyamideimide resin solution of Synthesis Example 2 was used, and the blending amount of the siloxane-modified polyamideimide resin was 30 parts by mass with respect to 100 parts by mass of the total epoxy resin. A resin composition varnish was obtained in the same manner as in Example 1, except that the NMP solution of the siloxane-modified polyamideimide resin of Synthesis Example 2 (resin solid content: 30% by mass) was blended.

  Using the obtained resin composition varnish, the prepreg and double-sided copper clad laminate of Example 2 were prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.

(Example 3)
Instead of the siloxane-modified polyamideimide resin solution of Synthesis Example 1, the siloxane-modified polyamideimide resin solution of Synthesis Example 3 was used, and the amount of the siloxane-modified polyamideimide resin was 8 parts by mass with respect to 100 parts by mass of the total epoxy resin. A resin composition varnish was obtained in the same manner as in Example 1 except that the NMP solution of siloxane-modified polyamideimide resin of Synthesis Example 3 (resin solid content: 32% by mass) was blended.

  Using the obtained resin composition varnish, the prepreg and double-sided copper clad laminate of Example 3 were prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.

Example 4
Instead of the siloxane-modified polyamideimide resin solution of Synthesis Example 1, the siloxane-modified polyamideimide resin solution of Synthesis Example 4 was used, and the blending amount of the siloxane-modified polyamideimide resin was 20 parts by mass with respect to 100 parts by mass of the total epoxy resin. A resin composition varnish was obtained in the same manner as in Example 1 except that the NMP solution of the siloxane-modified polyamideimide resin of Synthesis Example 4 (resin solid content: 35% by mass) was blended.

  Using the obtained resin composition varnish, the prepreg and double-sided copper-clad laminate of Example 4 were produced and evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.

(Example 5)
Instead of the NMP solution of the siloxane-modified polyamideimide resin of Synthesis Example 1, “KS-6600” (trade name, manufactured by Hitachi Chemical Co., Ltd., resin solid content 30.2 mass%, weight) Average molecular weight 95000), and the NMP solution of the siloxane-modified polyamideimide resin (resin solid content 30.30) so that the blending amount of the siloxane-modified polyamideimide resin is 20 parts by mass with respect to 100 parts by mass in total of the epoxy resin. Resin composition varnish was obtained in the same manner as in Example 1 except that 2% by mass) was added.

  Using the obtained resin composition varnish, the prepreg and double-sided copper-clad laminate of Example 5 were prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.

(Example 6)
Instead of the siloxane-modified polyamideimide resin solution of Synthesis Example 1, the siloxane-modified polyamideimide resin solution of Synthesis Example 5 was used, and the amount of the siloxane-modified polyamideimide resin was 40 parts by mass with respect to 100 parts by mass of the total epoxy resin. A resin composition varnish was obtained in the same manner as in Example 1 except that the NMP solution of the siloxane-modified polyamideimide resin of Synthesis Example 5 (resin solid content: 32% by mass) was blended.

<Preparation of prepreg>
The resin composition varnish prepared above was impregnated into a glass cloth having a thickness of 20 μm (trade name “WEX-1027” manufactured by Asahi Schavel Co., Ltd.), heated and dried at 150 ° C. for 15 minutes, and a resin content of 72 A mass% prepreg was obtained.

<Production of double-sided copper-clad laminate>
Four prepregs produced in the same manner as described above are laminated to form a laminate, and a copper foil having a thickness of 18 μm (Furukawa Metal Co., Ltd., trade name “F3-WS-18” or “F0-WS” is formed on both sides of the laminate. −18 ”) is laminated so that the adhesive surface is aligned with the prepreg, and heated and pressurized under the press conditions of 180 ° C., 90 minutes, 4.0 MPa, and two types of the double-sided copper-clad laminate of Example 1 (as copper foil) "F3-WS-18" and "F0-WS-18") were obtained.

  The prepreg and double-sided copper clad laminate obtained in Example 6 were evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2. The following bendability was also evaluated.

(6) Bendability Copper of the obtained double-sided copper-clad laminate was removed by etching, and this was used as a test substrate. A pin gauge with a radius of curvature of 0.10 mm, 0.38 mm, and 0.80 mm is brought into contact with the main surface inside the bent portion of the test substrate, and the test substrate is bent 90 degrees along the pin gauge. The bendability was evaluated based on the presence or absence of cracks or breaks in the test substrate. The results are shown in Table 2. In addition, the case where a crack generation and a fracture | rupture generation | occurrence | production are not seen is shown by "90 degree OK", and the case where a crack generation | occurrence | production or fracture | rupture generation | occurrence | production is seen is shown by "NG".

(Example 7)
A resin composition varnish was obtained in the same manner as in Example 2.

<Preparation of prepreg>
The resin composition varnish prepared above was impregnated into a glass cloth having a thickness of 20 μm (trade name “WEX-1027” manufactured by Asahi Sebel Co., Ltd.), heated and dried at 150 ° C. for 15 minutes, and a resin content of 74 A mass% prepreg was obtained.

<Production of double-sided copper-clad laminate>
Four prepregs produced in the same manner as described above are laminated to form a laminate, and a copper foil having a thickness of 18 μm (Furukawa Metal Co., Ltd., trade name “F3-WS-18” or “F0-WS” is formed on both sides of the laminate. −18 ”) is laminated so that the adhesive surface is aligned with the prepreg, and heated and pressurized under the press conditions of 180 ° C., 90 minutes, 4.0 MPa, and two types of the double-sided copper-clad laminate of Example 1 (as copper foil) "F3-WS-18" and "F0-WS-18") were obtained.

  The prepreg and double-sided copper-clad laminate obtained in Example 7 were evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2. In addition, the above-described bending property was also evaluated.

(Comparative Example 1)
Instead of the siloxane-modified polyamideimide resin solution of Synthesis Example 1, the siloxane-modified polyamideimide resin solution of Comparative Synthesis Example 1 was used, and the amount of the siloxane-modified polyamideimide resin was 10 parts by mass with respect to 100 parts by mass of the total epoxy resin. The resin composition varnish was prepared in the same manner as in Example 1 except that the NMP solution of the siloxane-modified polyamideimide resin of Comparative Synthesis Example 1 (resin solid content 35 mass%, weight average molecular weight 129000) was blended so as to obtain a ratio. Although preparation was attempted, the polyamideimide resin was separated and a resin composition varnish could not be obtained.

(Comparative Example 2)
Instead of the siloxane-modified polyamideimide resin solution of Synthesis Example 1, the siloxane-modified polyamideimide resin solution of Comparative Synthesis Example 2 was used, and the blending amount of the siloxane-modified polyamideimide resin was 20 parts by mass with respect to 100 parts by mass of the total epoxy resin. A resin composition varnish was obtained in the same manner as in Example 1 except that the NMP solution (resin solid content: 30% by mass) of the siloxane-modified polyamideimide resin of Comparative Synthesis Example 2 was blended so as to obtain a ratio.

  Using the obtained resin composition varnish, the preparation and evaluation of the prepreg and double-sided copper-clad laminate of Comparative Example 2 were performed in the same manner as in Example 1. The evaluation results are shown in Table 3. In the evaluation of impact resistance and thermal shock resistance, the printed circuit board of Comparative Example 2 was partially broken. In addition, cracks were observed in the resin in the vicinity of the disconnected portion.

(Comparative Example 3)
Instead of the siloxane-modified polyamideimide resin solution of Synthesis Example 1, the siloxane-modified polyamideimide resin solution of Synthesis Example 2 was used, and the compounding amount of the siloxane-modified polyamideimide resin was 0.5 parts by mass with respect to a total of 100 parts by mass of the epoxy resin. A resin composition varnish was obtained in the same manner as in Example 1 except that the NMP solution of the siloxane-modified polyamideimide resin of Synthesis Example 2 (resin solid content: 30% by mass) was blended so that the ratio was as follows.

  Using the obtained resin composition varnish, the prepreg and double-sided copper-clad laminate of Comparative Example 3 were prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3. In the evaluation of impact resistance and thermal shock resistance, the printed circuit board of Comparative Example 3 was partially broken. In addition, cracks were observed in the resin in the vicinity of the disconnected portion.

(Comparative Example 4)
Instead of the siloxane-modified polyamideimide resin solution of Synthesis Example 1, the siloxane-modified polyamideimide resin solution of Synthesis Example 2 was used, and the blending amount of the siloxane-modified polyamideimide resin was 60 parts by mass with respect to 100 parts by mass of the total epoxy resin. A resin composition varnish was obtained in the same manner as in Example 1, except that the NMP solution of the siloxane-modified polyamideimide resin of Synthesis Example 2 (resin solid content: 30% by mass) was blended.

  Using the obtained resin composition varnish, in the same manner as in Example 1, the preparation and evaluation of the prepreg and double-sided copper-clad laminate of Comparative Example 4 were performed. The evaluation results are shown in Table 3.

  As shown in Tables 1 and 2, no dust generation was observed in the prepregs of Examples 1 to 7, while dust generation was observed in the prepregs of Comparative Examples 2 and 3. Moreover, it was confirmed that the copper clad laminated board of Examples 1-7 shows a favorable result about all of solder heat resistance, copper foil adhesive strength, thermal shock resistance, and dust generation resistance. In addition, about the copper foil adhesive strength of the copper clad laminated board of Examples 1-7, when F3-WS-18 (peeling strength 1) is used, it is 0.8-1.2 kN / m, F0-WS-18. It was confirmed that a strength of 0.6 to 0.8 kN / m was obtained when (Peel strength 2) was used. Moreover, the printed circuit board produced using the copper-clad laminates of Examples 1 to 7 had a resistance change rate of + 5% or less in both the 1000-drop impact resistance test and the 1000-cycle thermal shock test. It was confirmed that there was.

Moreover, as shown in Table 3, the copper clad laminate of Comparative Example 4 was blistered in the solder heat resistance test at 260 ° C. and 288 ° C., and this blister was voided in the resin layer of the copper clad laminate. Therefore, the present inventors consider that the resin composition varnish is caused by insufficient impregnation into the fiber base material.

1 is a schematic cross-sectional view showing an embodiment of a prepreg according to the present invention. It is a fragmentary sectional view showing one embodiment of a metal foil tension laminate sheet concerning the present invention. It is a fragmentary sectional view showing one embodiment of a printed circuit board concerning the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 3 ... Fiber reinforced resin layer, 10 ... Metal foil, 30 ... Board | substrate, 100 ... Prepreg, 200 ... Metal foil tension laminated board, 300 ... Printed circuit board, 313a, 313b, 323a, 323b ... Circuit, 315 ... Inner layer circuit board, 311, 321 a, 321 b... Through-hole, 412, 322 a, 322 b... Conductor, 310, 320 a, 320 b.

Claims (8)

A fiber base material, and a resin composition impregnated in the fiber base material,
The resin composition includes an epoxy resin having two or more glycidyl groups, and a polyamideimide resin having a weight average molecular weight of 70000 or more and 120,000 or less,
The prepreg whose content of the said polyamidoimide resin in the said resin composition is 1-50 mass parts with respect to 100 mass parts of said epoxy resins.   The prepreg according to claim 1, wherein the polyamideimide resin is a siloxane-modified polyamideimide.   The polyamide-imide resin is a siloxane-modified polyamide-imide obtained by reacting a diimide dicarboxylic acid component containing a reaction product obtained by reacting siloxane diamine and trimellitic anhydride with an aromatic diisocyanate component. The prepreg according to claim 1.   The polyamidoimide resin is obtained by reacting a diimide dicarboxylic acid component containing a reaction product obtained by reacting a mixture of a diamine having an aromatic ring and a siloxane diamine with trimellitic anhydride, and an aromatic diisocyanate component. The prepreg according to claim 1, which is a siloxane-modified polyamideimide obtained. The polyamide-imide resin is
Diimide dicarboxylic acid represented by the following general formula (1) and the following general formula (1) obtained by reacting a mixture of diamine and siloxane diamine having three or more aromatic rings, or siloxane diamine and trimellitic anhydride. A diimide dicarboxylic acid component containing a diimide dicarboxylic acid represented by 2) or a diimide dicarboxylic acid component containing a diimide dicarboxylic acid represented by the following general formula (2);
An aromatic diisocyanate component represented by the following general formula (3);
The prepreg according to claim 1, wherein the prepreg is a siloxane-modified polyamideimide obtained by reacting.

[In formula (1), R ¹ represents a divalent organic group represented by the following general formula (1-1).

{In Formula (1-1), X is

}]

[In formula (2), R ² represents a divalent organic group represented by the following general formula (2-1).

{In Formula (2-1), R ³ and R ⁴ represent a divalent organic group, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group or a substituted or unsubstituted phenyl group. Represents a group, and n represents an integer of 1 to 50. }]

[In Formula (3), R ⁹ is

] The siloxane-modified polyamideimide is
A diamine component having a mixing ratio of diamine (a) having three or more aromatic rings and siloxane diamine (b) of a / b = 99.9 / 0.1 to 0/100 molar ratio; Trimellitic acid, [total number of moles of component (a) and component (b)] / [number of moles of trimellitic anhydride] = 1.0 / 2.0 to 1.0 / 2.2 In the diimide dicarboxylic acid component containing the diimide dicarboxylic acid represented by the general formula (1) and the diimide dicarboxylic acid represented by the general formula (2), obtained by reacting at a molar ratio of A diimide dicarboxylic acid component comprising the diimide dicarboxylic acid shown, and
An aromatic diisocyanate component represented by the general formula (3);
[The total number of moles of the component (a) and the component (b)] / [The number of moles of the aromatic diisocyanate component] = 1.0 / 1.0 to 1.0 / 1.5 The prepreg according to claim 5, which is a siloxane-modified polyamideimide obtained.   A laminate obtained by heating and pressing a predetermined number of the prepregs according to claim 1. A metal foil-clad laminate comprising: a substrate obtained by heating and pressing a predetermined number of the prepregs according to any one of claims 1 to 6; and a metal foil provided on one side or both sides of the substrate. Board.

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