JP5200565B2 - Printed wiring board and electronic device - Google Patents

Description

  The present invention relates to an electronic device including a printed wiring board and a folded printed wiring board.

  The printed wiring board can be obtained by subjecting a prepreg having an electrically insulating resin composition or the like as a matrix to heating and pressing. When the printed wiring board is formed by a subtractive method, a metal foil-clad laminate is usually used. This metal foil-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 electrical insulating resin, thermosetting resins such as phenol resin, epoxy resin, polyimide resin, bismaleimide-triazine resin, etc. are widely used, but depending on the required characteristics, fluorine resin, polyphenylene ether resin, etc. A thermoplastic resin such as is sometimes used.

  Such printed wiring boards are becoming smaller and higher in density with the spread of information terminal devices such as personal computers and mobile phones. The mounting form has shifted from the pin insertion type to the surface mounting type, and further to the area array type represented by BGA (ball grid array) using a plastic substrate. In a printed wiring board that directly mounts a bare chip such as a BGA, the connection between the chip and the printed wiring board is generally performed by wire bonding by thermosonic bonding. Therefore, since the printed wiring board on which the bare chip is mounted is exposed to a high temperature of 150 ° C. or higher, it is required to have heat resistance.

  Also, the printed wiring board may be required to have a so-called repair property in which a chip once mounted is removed. Such a printed wiring board is subjected to the same level of heat as that during chip mounting when the chip is removed, and then heat treated again for chip mounting. Accordingly, printed wiring boards that require repairability are also required to have cyclic thermal shock resistance at high temperatures.

  Under such circumstances, in order to improve thermal shock resistance, reflow resistance, and crack resistance, a prepreg impregnated with a resin composition containing polyamideimide as an essential component in a fiber base (see, for example, Patent Document 1), A heat-resistant base material (for example, see Patent Document 2) in which a fiber base material is impregnated with a resin composition composed of a silicone-modified polyimide resin and a thermosetting resin has been proposed.

  On the other hand, with the miniaturization and high performance of electronic devices, it is necessary to store printed wiring boards with component mounting in a limited space, and thinning of printed wiring boards is required. ing. In order to meet such a demand, a thin substrate for a printed wiring board has been developed, and a glass cloth having a thickness of 10 μm is being supplied. It has been proposed to improve the bending characteristics of a printed wiring board by combining these thin fiber base materials with a flexible resin.

Moreover, in order to improve the storage property of a printed wiring board, the method of arrange | positioning a some printed wiring board in multiple stages and connecting each other with a wire harness or a flexible wiring board is taken. In addition, a rigid-flex substrate in which a flexible substrate based on polyimide and a conventional rigid substrate are multilayered is used. As described above, the printed wiring board that can be bent arbitrarily plays an important role in miniaturization and high performance of electronic devices.
JP 2003-55486 A JP-A-8-193139

  By the way, electronic devices are being further miniaturized and improved in performance, and the printed wiring board can be bent arbitrarily and has excellent dimensional stability so that the printed wiring board can be housed in the housing at a higher density. A board is sought.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a printed wiring board that can be bent arbitrarily and has sufficient dimensional stability and has sufficiently improved folding resistance. To do. Moreover, an object of this invention is to provide an electronic device provided with the said printed wiring board bent.

  In order to achieve the above object, in the present invention, a printed wiring board that is bent in a predetermined bending direction, which is formed on a fiber base material containing first fibers arranged in a first direction, and the fiber base material A printed wiring board that is arranged so that an angle formed between the first direction and the bending direction is 30 to 60 degrees.

  Since such a printed wiring board has a fiber base material, it can be arbitrarily bent and has sufficient dimensional stability. Further, the folding resistance is sufficiently improved. The present inventors infer the reason why such an effect is obtained as follows.

FIG. 3 is a top view of a conventional printed wiring board that can be bent. When the conventional printed wiring board to be bent as shown in FIG. 3 is bent in a predetermined bending direction, the angle between the direction in which the fibers are arranged and the bending direction is usually 0 degrees and / or 90 degrees. For example, in FIG. 3, the angle θ ₁ formed by the arrangement direction of the fibers 76 and the bending direction B is 90 degrees, and the angle formed by the arrangement direction of the fibers 78 and the bending direction B is 0 degrees. When the angle formed is 0 degrees, that is, when the bending direction and the fiber arrangement direction are parallel, when the printed wiring board is bent, the fiber is arranged on the side of the surface that is bent and protruded (in FIG. 3, the fiber 78), a large tensile stress is applied, and the fiber tends to break easily. Further, in the case of fibers (fiber 76 in FIG. 3) in which the formed angle is 90 degrees, the bending strength is not sufficient and the printed wiring board tends to break when bent.

  However, in the printed wiring board of the present invention, the fibers are arranged so that the angle formed between the bending direction and the fiber arranging direction is 30 to 60 degrees. The tensile stress applied to the first fibers arranged in the direction 1 can be reduced. Therefore, it is considered that the folding resistance is sufficiently excellent. The “bending direction” in the present invention refers to a direction that is bent when the printed wiring board is mounted on an electronic device in a bent state, for example, and is a direction perpendicular to the bending line in the printed wiring board. . Further, the “angle formed between the first direction and the bending direction” refers to an acute angle among the angles measured in a plane parallel to the first direction and the bending direction.

  Moreover, in this invention, it is preferable that a fiber base material further contains the 2nd fiber arranged in the 2nd direction which cross | intersects a 1st direction. Since such a printed wiring board further contains the second fiber in which the fiber base material is arranged in the second direction different from the first direction, the tensile stress generated when it is bent is It can disperse | distribute to a 1st fiber and a 2nd fiber. Accordingly, the folding resistance is further sufficiently improved. Moreover, the printed wiring board provided with the fiber base material which has the 1st fiber and the 2nd fiber which were respectively arranged in two mutually different directions is excellent also in the tolerance with respect to a twist.

  Moreover, in this invention, it is preferable that the 2nd fiber is arranged so that the angle which the said 2nd direction and the said bending direction make may be 30 to 60 degree | times. In such a wiring board, since the angle formed between the first direction and the bending direction and the angle formed between the second direction and the bending direction are both 30 to 60 degrees, when the printed wiring board is bent, The tensile stress is uniformly dispersed by the first fiber and the second fiber. Therefore, folding resistance can be further improved. The “angle formed between the second direction and the bending direction” refers to an acute angle among the angles measured in a plane parallel to the second direction and the bending direction.

  In the printed wiring board of the present invention, the fiber is preferably a glass cloth, and the thickness of the fiber base material is preferably 50 μm or less. If the fiber is a glass cloth, the dimensional change accompanying temperature, moisture absorption, etc. can be reduced. Moreover, if thickness is 50 micrometers or less, folding resistance can be improved further.

  In the present invention, the fiber base material is preferably impregnated with a thermosetting resin. Thereby, folding resistance can be further improved.

  In this invention, it is preferable that the said thermosetting resin contains resin which has a glycidyl group. Thereby, the heat resistance and thermal shock resistance of the printed wiring board can be improved.

  Moreover, in this invention, it is preferable that the said thermosetting resin contains resin which has an amide group. Thereby, the flexibility, heat resistance, dust resistance, and thermal shock resistance of the printed wiring board can be improved.

  Moreover, in this invention, it is preferable that the said thermosetting resin contains the polyamidoimide resin which has a siloxane bond. Thereby, the flexibility, heat resistance, dust resistance, and thermal shock resistance of the printed wiring board can be improved.

  Moreover, in this invention, it is preferable that the said thermosetting resin contains an acrylic resin. Thereby, flexibility, heat resistance, dust generation resistance, and thermal shock resistance can be improved.

  The present invention provides an electronic device including the printed wiring board bent in a predetermined bending direction. Since such an electronic device includes the printed wiring board having the above characteristics, problems such as disconnection and breakage can be sufficiently prevented.

  According to the present invention, it is possible to obtain a printed wiring board that can be arbitrarily bent, has sufficient dimensional stability, and has sufficiently improved folding resistance. Moreover, an electronic device provided with the printed wiring board which has the said characteristic bent can be obtained.

  In the following, preferred embodiments of the present invention will be described with reference to the drawings as the case may be. In the description of the drawings, the same reference numerals are used for the same or equivalent elements, and duplicate descriptions are omitted.

  FIG. 1 is a top view showing a preferred embodiment of the printed wiring board of the present invention. The printed wiring board 100 includes a bent portion 40 and a pair of non-bent portions 20 so as to sandwich the bent portion 40.

  The bent portion 40 includes a fiber base material including a first fiber 6 and a second fiber 8 orthogonal to the first fiber 6, and a thermosetting resin impregnated in the fiber base material. And a conductor 4 provided on one surface of the fiber base layer 2. The first fibers 6 are arranged in the first direction A, and the second fibers 8 are arranged in the second direction C. In the fiber base layer 2, a plurality of first fibers and second fibers are arranged at predetermined intervals in a direction (thickness direction) perpendicular to FIG.

  The non-bent portion 20 is a rigid board (rigid printed wiring board) that is normally used in electronic devices and the like. A pair of rigid printed wiring boards provided so as to sandwich the bent portion 40 are electrically connected to each other by the bent portion 40.

  As a fiber base material in the fiber base material layer 2, fiber base materials, such as a woven fabric and a nonwoven fabric, which are used for a normal metal foil-clad laminate and a multilayer printed wiring board can be used. The material of the fiber base material, that is, the material of the first fiber 6 and the second fiber 8 is inorganic such as glass, alumina, asbestos, boron, silica alumina glass, silica glass, tyranno, silicon carbide, silicon nitride, zirconia. Fibers, organic fibers such as aramid, polyetheretherketone, polyetherimide, polyethersulfone, carbon and cellulose, and mixed papers thereof are preferred, and among these, glass cloth is particularly preferred. As the fiber substrate in the present invention, a glass cloth woven fabric is most preferable. The fiber may be a fiber having a relatively short length in the longitudinal direction such as a filler.

  The thickness of the fiber base material is preferably 50 μm or less. By using the glass cloth having such a thickness, the flexibility of the bent portion 40 of the printed wiring board 100 can be further improved.

  Examples of the conductor 4 include ordinary metals such as copper and silver. From the viewpoint of improving the bendability, the thickness of the conductor 4 is preferably 1 to 30 μm.

  The printed wiring board 100 is bent in a bending direction B along a folding line D (so that the upper side or the lower side in FIG. 1 has a convex shape), and is disposed in, for example, an electronic device. The fold line D usually refers to a fold line (fold line) generated when the fold line D is bent. A direction perpendicular to the fold line is a fold direction B. However, when a fold line does not occur, for example, a direction perpendicular to a ridge line generated by bending can be set as a fold direction B.

As shown in FIG. 1, the first direction A, in a plane parallel to the second direction C and bending direction B, the direction B bent to the first direction A and an angle theta _1, the second the direction B and folding direction C at an angle theta _2. In the present invention, both the angle θ ₁ and the angle θ ₂ are acute angles, and at least one of the angle θ ₁ and the angle θ ₂ is 30 to 60 degrees. Both the angle θ ₁ and the angle θ ₂ are preferably 30 to 60 degrees, more preferably 40 to 50 degrees, and still more preferably 45 degrees. As the angle θ ₁ and the angle θ ₂ approach 45 degrees, the folding resistance and the resistance to torsion can be improved. In addition, the said angle (theta) ₁ and angle (theta) ₂ can be confirmed by observing the one surface (upper surface) of a printed wiring board with an optical microscope, for example.

  In a plane parallel to the first direction and the second direction, the angle formed by the first direction and the second direction is preferably 30 to 90 degrees, and more preferably 60 to 90 degrees. 90 degrees is more preferable. The angle formed is an angle of 90 degrees or less on a plane parallel to the first direction and the second direction.

  FIG. 2 is a side view of the folded printed wiring board. In the wiring board 100 bent as shown in FIG. 2, since the tensile stress generated in the vicinity of the ridge line is dispersed in the first fiber and the second fiber included in the fiber base material 2, the bending resistance is improved. Excellent. Moreover, since the fiber base material contained in the fiber base material layer 2 has the 1st fiber and 2nd fiber which were arranged in two mutually different directions, the fiber base material which consists only of the fiber arranged in one direction Compared to, it is excellent in resistance to twisting.

  The printed wiring board 100 of this embodiment can be formed using a prepreg in which a fiber base material is impregnated with a thermosetting resin.

  As the thermosetting resin impregnated in the fiber base material, an insulating resin generally used in the printed wiring board field is used, and is obtained by curing the resin composition. Examples of the thermosetting resin include epoxy resins, polyimide resins, unsaturated polyester resins, polyurethane resins, bismaleimide resins, triazine-bismaleimide resins, phenol resins, and the like.

  The thermosetting resin is preferably a resin having a glycidyl group, and more preferably includes an epoxy resin. Epoxy resins include polyglycidyl ethers and phthalates obtained by reacting polychlorophenols such as bisphenol A, novolac phenolic resins, orthocresol novolac phenolic resins or polyhydric alcohols such as 1,4-butanediol with epichlorohydrin. Examples thereof include polyglycidyl esters obtained by reacting polybasic acids such as acid and hexahydrophthalic acid with epichlorohydrin, N-glycidyl derivatives of amines, amides or compounds having a heterocyclic nitrogen base, alicyclic epoxy resins, etc. It is done.

  By using an epoxy resin as the thermosetting resin, it can be cured at a temperature of 180 ° C. or lower. Moreover, thermal, mechanical, and electrical characteristics can be improved by using an epoxy resin. An epoxy resin having two or more glycidyl groups and its curing agent, an epoxy resin having two or more glycidyl groups and its curing accelerator, or an epoxy resin having two or more glycidyl groups and its curing agent and curing accelerator It is preferable to use it. The greater the number of glycidyl groups contained in the epoxy resin, the more preferable. In addition, the compounding quantity of the epoxy resin in a resin composition can be changed with the number of glycidyl groups. Generally, the more glycidyl groups contained in an epoxy resin, the more the amount of epoxy resin in the resin composition can be reduced.

  The curing agent used to cure the epoxy resin, the curing accelerator is not limited as long as it reacts with the epoxy resin or accelerates curing, for example, amines, imidazoles, polyfunctional phenols, Acid anhydrides can be used. As the amines, dicyandiamide, diaminodiphenylmethane, guanylurea and the like can be used. As the polyfunctional phenols, hydroquinone, resorcinol, bisphenol A and halogen compounds thereof, novolak type phenol resins and resol type phenol resins which are condensates with formaldehyde can be used. As acid anhydrides, phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic acid, or the like can be used. As the curing accelerator, alkyl group-substituted imidazole, benzimidazole and the like can be used as imidazoles.

  When using amines, the compounding quantity of the hardening | curing agent and hardening accelerator in a resin composition has the preferable quantity where the equivalent of the active hydrogen of an amine and the epoxy equivalent of an epoxy resin become substantially equal. When using imidazole as a curing accelerator, it is not simply an equivalent ratio with active hydrogen, and is usually 0.001 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin. Moreover, when using polyfunctional phenols and acid anhydrides, it is preferable that it is 0.6-1.2 equivalent of phenolic hydroxyl groups or carboxyl groups with respect to 1 equivalent of epoxy resins. If the blending amounts of these curing agents and curing accelerators are too small, uncured epoxy resin remains and Tg (glass transition temperature) tends to be low. On the other hand, when there are too many compounding quantities of a hardening | curing agent and a hardening accelerator, an unreacted hardening | curing agent and a hardening accelerator remain, and there exists a tendency for insulation to fall.

  The thermosetting resin (insulating resin) impregnated in the fiber base material of the present embodiment may contain a high molecular weight resin component for the purpose of improving flexibility and heat resistance. Examples of the high molecular weight resin component include polyamideimide resin and acrylic resin.

  As the polyamideimide resin, a siloxane-modified polyamideimide having a siloxane bond in the resin is preferable. In particular, a siloxane-modified polyamide obtained by reacting a mixture of diimide dicarboxylic acid obtained by reacting a mixture of diamine having two or more aromatic rings and siloxane diamine with trimellitic anhydride and aromatic diisocyanate. An imide resin is preferred.

  In the siloxane-modified polyamideimide having a siloxane structure in the molecule, the mixing molar ratio of the aromatic diamine a having 2 or more aromatic rings and the siloxane diamine b (a / b) is 99.9 / 0.1. It is preferably 0/100, more preferably a / b = 95/5 to 30/70, and even more preferably a / b = 90/10 to 40/60. If the mixing ratio of siloxane diamine b is too large, the Tg of the resin tends to decrease. Moreover, when the said mixing ratio decreases too much, when producing metal foil with resin, there exists a tendency for the amount of varnish solvent which remains in resin to increase.

  Examples of the aromatic diamine include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4- (3-aminophenoxy) phenyl] sulfone, and 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-aminophenoxy) benzene, 1,4- Bis (4-aminophenoxy) benzene, 2,2′-dimethylbiphenyl-4,4′-diamine, 2,2′-bis (trifluoro) Methyl) biphenyl-4,4′-diamine, 2,6,2 ′, 6′-tetramethyl-4,4′-diamine, 5,5′-dimethyl-2,2′-sulfonyl-biphenyl-4,4 '-Diamine, 3,3'-dihydroxybiphenyl-4,4'-diamine, (4,4'-diamino) diphenyl ether, (4,4'-diamino) diphenyl sulfone, (4,4'-diamino) benzophenone, (3,3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether and the like.

  As the siloxane diamine, for example, compounds represented by the following general formulas (1) to (4) can be used.

［式中、ｎは１〜５０の整数を示す。］

[Wherein n represents an integer of 1 to 50. ]

［式中、ｍは１〜５０の整数を示す。］

[Wherein, m represents an integer of 1 to 50. ]

［式中、ｋは１〜５０の整数を示す。］

[In formula, k shows the integer of 1-50. ]

［式中、ｑ及びｒは、それぞれ独立に１〜４０の整数を示し、且つ２≦ｑ＋ｒ＜５０である。］

[Wherein q and r each independently represent an integer of 1 to 40, and 2 ≦ q + r <50. ]

  Examples of the siloxane diamine represented by the general formula (1) include X-22-161AS (amine equivalent: 450), X-22-161A (amine equivalent: 840), and X-22-161B (amine equivalent: 1500). (Above, Shin-Etsu Chemical Co., Ltd., trade name), BY16-853 (amine equivalent: 650), BY16-853B (amine equivalent: 2200), (above, Toray Dow Corning Silicone Co., trade name), etc. It can be illustrated. As siloxane diamine represented by the general formula (4), X-22-9409 (amine equivalent 700), X-22-1660B-3 (amine equivalent 2200) (above, manufactured by Shin-Etsu Chemical Co., Ltd., trade name) ) Etc.

  As the aliphatic diamine for obtaining the siloxane-modified polyamideimide resin, a compound represented by the following general formula (5) can be used.

［式中、Ｘはメチレン基、スルホニル基、エーテル基、カルボニル基又は単結合を示し、Ｒ^１及びＲ^２はそれぞれ水素原子、アルキル基、フェニル基又は置換フェニル基を示し、ｐは１〜５０の整数を示す。］

[Wherein, X represents a methylene group, a sulfonyl group, an ether group, a carbonyl group or a single bond, R ¹ and R ² represent a hydrogen atom, an alkyl group, a phenyl group or a substituted phenyl group, respectively, and p represents 1 to 50 Indicates an integer. ]

As R < ¹ > and R < ² > in General formula (5), a hydrogen atom, a C1-C3 alkyl group, a phenyl group, and a substituted phenyl group are preferable. As a substituent of a substituted phenyl group, a C1-C3 alkyl group, a halogen atom, etc. can be illustrated.

  In the aliphatic diamine, X in the general formula (5) is preferably an ether group from the viewpoint of achieving both low elastic modulus and high Tg. Examples of such aliphatic diamines include Jeffamine D-400 (amine equivalent 400, manufactured by Mitsui Chemicals Fine Co., Ltd., trade name), Jeffamine D-2000 (amine equivalent 1000, manufactured by Mitsui Chemicals Fine Co., Ltd., commercial products). Name) etc. can be illustrated.

  The polyamideimide resin is preferably a polyamideimide resin containing 70 mol% or more of polyamideimide molecules containing 10 or more amide groups in one molecule. The content of the polyamidoimide molecule contained in the polyamidoimide resin is the chromatogram obtained from GPC (gel permeation chromatography) of polyamidoimide, and the number of moles of amide groups in the unit mass determined separately from this ( A). For example, from the number of moles of amide groups (A) contained in the polyamide-imide resin (a) g, the value calculated by the formula (10 × a / A) is used to obtain polyamide imide containing 10 amide groups in one molecule. The molecular weight (C) of the molecule. In this case, the ratio of the region where the number average molecular weight of the chromatogram obtained by GPC is not less than the molecular weight (C) is the content of polyamideimide molecules containing 10 or more amide groups. In addition, NMR, IR, hydroxamic acid-iron color reaction method, N-bromoamide method, etc. can be used for the determination method of the number of moles (A) of the amide group.

The above-mentioned measurement of GPC (gel permeation chromatography) can be performed with the following measuring apparatus and measurement conditions.
Detector: L-7490 (manufactured by Hitachi, Ltd.)
Column: GL-S300MDT-5 (manufactured by Hitachi Chemical Co., Ltd., two directly connected)
Eluent: DMF / THF mixture containing 0.60 M H ₃ PO ₄ and 0.30 M LiBr [DMF / THF = 1/1 (volume ratio)]
Measurement temperature: 30 ° C
Sample concentration: 0.2 mg / 1 ml
Injection volume: 100 μl
Pressure: 4MPa
Flow rate: 1 ml / min

  As the diisocyanate used in the production of the polyamideimide resin of the present invention, a compound represented by the following general formula (6) can be used.

［式中、Ｄは少なくとも１つの芳香環を有する２価の有機基、又は２価の脂肪族炭化水素基を示す。］

[Wherein, D represents a divalent organic group having at least one aromatic ring or a divalent aliphatic hydrocarbon group. ]

Examples of the divalent group represented by D in the general formula (6) include a group represented by —C ₆ H ₄ —CH ₂ —C ₆ H ₄ —, a tolylene group, a naphthylene group, a hexamethylene group, 2 , 2,4-trimethylhexamethylene group and at least one group selected from the group consisting of isophorone groups are preferable.

  As the diisocyanate represented by the general formula (6), aliphatic diisocyanate or aromatic diisocyanate can be used. Among these, it is preferable to use an aromatic diisocyanate, and it is more preferable to use an aliphatic diisocyanate and an aromatic diisocyanate in combination.

  Aromatic diisocyanates include 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, 2,4-tolylene dimer, and the like. It can be illustrated. Of these examples, MDI is preferably used. By using MDI as the aromatic diisocyanate, the flexibility of the resulting polyamideimide resin can be further improved.

  Examples of the aliphatic diisocyanate include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and isophorone diisocyanate.

  When the aromatic diisocyanate and the aliphatic diisocyanate are used in combination, it is preferable to add the aliphatic diisocyanate to about 5 to 10 mol% with respect to the aromatic diisocyanate. By using an aromatic diisocyanate and an aliphatic diisocyanate in combination, the heat resistance of the resulting polyamideimide resin can be further improved.

  As the acrylic resin, it is possible to use an acrylic acid monomer, a methacrylic acid monomer, acrylonitrile, an acrylic monomer having a glycidyl group, or a copolymer obtained by copolymerizing a plurality of these monomers. Although molecular weight is not specifically limited, It is preferable to use what the weight average molecular weight of standard polystyrene conversion calculated | required by GPC (gel permeation chromatography) is 300,000-1 million, and is 400,000-800,000. It is more preferable to use a certain one. In addition, the GPC measurement in this case can be performed by directly connecting three GMH XL (manufactured by Tosoh Corporation) and using THF as an eluent. Moreover, it is preferable to add and use an epoxy resin, a hardening | curing agent, and a hardening accelerator to these acrylic resins.

  An additive-type flame retardant can also be used for the purpose of improving flame retardancy. As the additive-type flame retardant, a filler containing phosphorus can be preferably used. As the phosphorus-containing filler, OP930 (manufactured by Clariant, trade name, phosphorus content: 23.5% by mass), HCA-HQ (manufactured by Sanko Co., Ltd., trade name, phosphorus content: 9.6% by mass), polyphosphorus Acid melamine PMP-100 (phosphorus content: 13.8 mass%), PMP-200 (phosphorus content: 9.3 mass%), PMP-300 (phosphorus content: 9.8 mass%) (above, Nissan Chemical brand name, product name, etc.).

  An example of a method for manufacturing the printed wiring board of the present embodiment will be described below.

  First, a varnish of a thermosetting resin composition is impregnated into a fiber base material and dried in a range of 80 ° C. to 180 ° C. to produce a prepreg. The production conditions of the prepreg are not particularly limited, but it is preferable that 80% by mass or more of the solvent used for the varnish is volatilized in the prepreg. There are no particular limitations on the production method, drying conditions, etc., the temperature during drying can be adjusted to 80 ° C. to 180 ° C., and the time can be adjusted in consideration of the gelling time of the varnish. The amount of impregnation of the varnish is preferably 30 to 80% by mass with respect to the total amount of the varnish solid and the fiber substrate.

  After obtaining a prepreg laminate by laminating a plurality of prepregs obtained in this manner as needed, copper foil is laminated on both sides or one side of the prepreg laminate and laminated by pressing to obtain a copper foil-clad laminate. be able to. A printed wiring board can be obtained by processing this with a normal photolithography method. The printed wiring board 100 can be obtained by electrically connecting such an arbitrarily bendable printed wiring board and a commonly used rigid wiring board by a normal method.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment. For example, in the said embodiment, although the fiber base material was comprised with two types of fibers from which the direction which mutually arranges differs, the fiber base material may be comprised only with the fiber which arranges in one direction. In this case, the effect of the present invention can be obtained by setting the angle between the direction in which the fibers are arranged and the bending direction to 30 to 60 degrees. Further, the fiber base material may include fibers arranged in other directions in addition to the first direction and the second direction. In this case, in the fiber base material, it is preferable that the angle formed by the direction in which the most densely arranged fibers (main fibers) are arranged and the bending direction is 30 to 60 degrees.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

(Varnish formulation example 1)
Methyl ethyl ketone solution of polyamideimide resin (manufactured by Hitachi Chemical Co., Ltd., trade name: KS9900B, resin solid content: 31.2 mass%) 22.44 kg and epoxy resin EPPN502H (trade name, manufactured by Nippon Kayaku Co., Ltd.) (Resin solid content: 50% by mass) 2.0 kg, HP4032D (Dainippon Ink Chemical Co., Ltd., trade name) 3.0 kg, NC3000 (Nippon Kayaku Co., Ltd., trade name) methyl ethyl ketone solution (resin (Solid content: 50% by mass) 1.0 kg and 8.0 g of 1-cyanoethyl-2-ethyl-1-methylimidazole were mixed and stirred for about 1 hour until the resin component became uniform. The resin composition varnish was obtained by standing at room temperature (25 ° C.) for 24 hours.

(Varnish formulation example 2)
Methyl ethyl ketone solution of polyamideimide resin (manufactured by Hitachi Chemical Co., Ltd., trade name: KS9900B, resin solid content: 31.2 mass%) 22.44 kg and epoxy resin EPPN502H (trade name, manufactured by Nippon Kayaku Co., Ltd.) (Resin solid content: 50% by mass) 2.0 kg, HP4032D (Dainippon Ink Chemical Co., Ltd., trade name) 3.0 kg, NC3000 (Nippon Kayaku Co., Ltd., trade name) methyl ethyl ketone solution (resin (Solid content 50% by mass) 1.0 kg and 1-cyanoethyl-2-ethyl-1-methylimidazole 8.0 g, OP930 (manufactured by Clariant, trade name) 1.0 kg, HP360 (Showa) (Product name) 1.5 kg made by Denko Co., Ltd. was added and stirred for about 3 hours until the resin component became uniform. Time was allowed to stand at room temperature (25 ° C.) to obtain a resin composition varnish.

(Varnish formulation example 3)
EPICLON 153 (trade name, manufactured by Dainippon Ink Co., Ltd.) as an epoxy resin, 3.4 kg as a curing agent, 1.81 kg (trade name, manufactured by Teijin Chemicals Ltd.), and 1-cyanoethyl-2 as a curing accelerator -After dissolving 10.0 g of phenylimidazole in 6.0 kg of methyl isobutyl ketone, a methyl ethyl ketone solution (resin content: 15% by mass) of acrylic resin HTR-860-P3 (trade name, manufactured by Nagase ChemteX Corporation) ) 2.87 kg was added and stirred for 1 hour until the resin component was uniform. Then, it left still at room temperature (25 degreeC) for 24 hours for defoaming, and obtained the resin composition varnish.

(Varnish formulation example 4)
BREN-S (trade name, manufactured by Nippon Kayaku Co., Ltd.) 3.0 kg as an epoxy resin, FG-2000 (trade name, manufactured by Teijin Chemicals Ltd.) 1.81 kg as a curing agent, and 1-cyanoethyl as a curing accelerator After dissolving 10.0 g of 2-ethyl-1-methylimidazole in 6.0 kg of methyl isobutyl ketone, a methyl ethyl ketone solution (resin) of acrylic resin HTR-860-P3 (trade name, manufactured by Nagase ChemteX Corporation) (Content: 15% by mass) 2.87 kg was added and stirred for 1 hour until the resin component became uniform. Then, it left still at room temperature (25 degreeC) for 24 hours for defoaming, and obtained the resin composition varnish.

(Varnish formulation example 5)
A BAPP (2.2-bis [4] as a diamine having two or more aromatic rings is added to a 25-liter separable flask equipped with a faucet connected to a reflux condenser, a 25-ml water quantitative receiver, a thermometer, and a stirrer. -(4-aminophenoxy) phenyl] propane) 246.0 g (0.60 mol), as a siloxane diamine, X-22-9409 (manufactured by Shin-Etsu Silicone, trade name, amine equivalent: 700) 280.0 g (0.40 mol) , TMA (trimellitic anhydride) 393.6 g (2.05 mol) and NMP (N-methyl-2-pyrrolidone) 2383 g as an aprotic polar solvent were charged and stirred at 80 ° C. for 30 minutes. Then, 500 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and then the temperature was raised and refluxed at about 160 ° C. for 2 hours. After confirming that more than 36.0 ml of water was distilled from the moisture determination receiver and that no new water was observed, the temperature was raised to about 190 ° C. to remove toluene. Thereafter, the obtained solution was returned to room temperature, and 275.0 g (1.10 mol) of MDI (4,4′-diphenylmethane diisocyanate) as an aromatic diisocyanate was added to the solution, and reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of polyamideimide resin was obtained.

  2.26 kg of NMP solution of the obtained polyamideimide resin (resin solid content: 31.1 mass%), EPPN502H (trade name, manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin 0.2 kg (resin solid content of 50 mass%) Methyl ethyl ketone solution), HP4032D (Dainippon Ink Chemical Co., Ltd., trade name) 0.3 kg, NC3000 (manufactured by Nippon Kayaku Co., Ltd., trade name) 0.5 kg (resin solid content: 50 mass% methyl ethyl ketone solution), and 0.8 g of 1-cyanoethyl-2-ethyl-1-methylimidazole was added, and 0.1 kg of OP930 (manufactured by Clariant, trade name) and 0.15 kg of HP 360 (manufactured by Showa Denko KK, trade name) were added to the resin. The mixture was stirred for about 3 hours until it became uniform. Then, it left still at room temperature (25 degreeC) for 24 hours for defoaming, and obtained the resin composition varnish.

(Varnish formulation example 6)
BAPP (2.2-bis [4] as a diamine having two or more aromatic rings was added to a 25-mL water quantitative receiver with a cock connected to a reflux condenser, a thermometer, and a 1-liter separable flask equipped with a stirrer. -(4-Aminophenoxy) phenyl] propane) 348.5 g (0.85 mol), X-22-21660B-3 (trade name, amine equivalent 2200, manufactured by Shin-Etsu Silicone) as a siloxane diamine 330.0 g (0.15 mol) ), TMA (trimellitic anhydride) 393.6 g (2.05 mol), and 2600 g of NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent were charged and stirred at 80 ° C. for 30 minutes. Then, 500 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and then the temperature was raised and refluxed at about 160 ° C. for 2 hours. After confirming that more than 36.0 ml of water was distilled from the moisture determination receiver and that no new water was observed, the temperature was raised to about 190 ° C. to remove toluene. Thereafter, the obtained solution was returned to room temperature, and 275.0 g (1.10 mol) of MDI (4,4′-diphenylmethane diisocyanate) as an aromatic diisocyanate was added to the solution, and reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of polyamideimide resin was obtained.

  2.24 kg of NMP solution of the obtained polyamideimide resin (resin solid content: 31.2 mass%), EPPN502H (trade name, manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin 0.2 kg (resin solid content of 50 mass%) Methyl ethyl ketone solution), HP4032D (Dainippon Ink Chemical Co., Ltd., trade name) 0.3 kg, NC3000 (manufactured by Nippon Kayaku Co., Ltd., trade name) 0.5 kg (methyl ethyl ketone solution having a resin solid content of 50% by mass), and 1 -0.8 g of cyanoethyl-2-ethyl-1-methylimidazole was added, and 0.1 kg of OP930 (manufactured by Clariant, trade name) and 0.15 kg of HP 360 (manufactured by Showa Denko KK, trade name) were added, and the resin was added. Stir for about 3 hours until uniform. Then, it left still at room temperature (25 degreeC) for 24 hours for defoaming, and obtained the resin composition varnish.

(Preparation of prepreg)
On both main surfaces of glass cloth WEX-1027 (manufactured by Asahi Sebel Co., Ltd., trade name, thickness 19 μm), the resin composition varnish produced in varnish compounding example 1 is dried so that the total thickness after drying is 55 μm. The prepreg (P1) having a resin content of 71 mass% was obtained by applying with a vertical coating machine and heating and drying in a drying furnace at 100 to 140 ° C. for a residence time of 10 minutes. Similarly, prepregs (P2 to P6) having a resin content of 71% by mass were obtained using the respective resin composition varnishes prepared in varnish formulation examples 2 to 6.

(Production of resin film)
On a polyethylene terephthalate (PET) film (manufactured by Teijin Ltd., trade name: PUREX 31), the resin composition varnish produced in varnish compounding example 1 is applied with a die coater so that the thickness after drying becomes 50 μm. The resin film F1 was obtained by heating and drying in a drying furnace at 100 to 140 ° C. for a residence time of 5 minutes. Similarly, resin films (F2 to F6) were obtained using the respective resin composition varnishes prepared in varnish formulation examples 2 to 6.

( Reference Example 1)
The prepreg P1 is sandwiched between a pair of electrolytic copper foils having a thickness of 12 μm (trade name: HLA-12, manufactured by Nippon Electrolytic Co., Ltd.), and the electrolysis is performed on both main surfaces (surfaces perpendicular to the thickness direction) of the prepreg P1. Each copper foil was laminated, and pressed on the conditions of a heating rate of 5 ° C./min, a forming temperature of 230 ° C., a forming pressure of 4 MPa, a forming time of 70 minutes, and a vacuum degree of 40 hPa, to produce a double-sided copper foil-clad laminate.

  On one main surface (surface perpendicular to the thickness direction) of this double-sided copper foil-clad laminate, a conductive pattern circuit having a line width of 50 μm was formed by etching. At this time, on the plane parallel to the main surface, the conduction pattern is such that the angle between the direction in which both glass fibers are arranged (longitudinal direction) and the longitudinal direction of the conduction pattern circuit (conduction direction) is 45 degrees. A circuit was formed. The entire surface of the surface opposite to the surface on which the conductive pattern circuit was manufactured was etched to remove the copper foil, and a substrate material having a conductive pattern circuit on one main surface was manufactured.

  On the surface on which the conductive pattern of the substrate material is formed, a resin film F1 and an electrolytic copper foil (manufactured by Nippon Electrolytic Co., Ltd., trade name: HLA-12) are sequentially laminated, and the heating rate is 5 ° C./min, molding temperature. Pressing was performed at 230 ° C., a molding pressure of 4 MPa, a molding time of 70 minutes, and a degree of vacuum of 40 hPa. The copper foil on the surface of the laminate obtained by pressing was removed by etching all over to obtain an evaluation substrate in which the conductive pattern circuit was coated with a resin.

( Reference Examples 2-4, Examples 5-6 )
Evaluation boards were obtained in the same manner as in Reference Example 1 except that prepregs P2 to P6 were used instead of prepreg P1 and resin films F2 to 6 were used instead of resin film F1.

( Reference Example 7)
The electrolytic copper foil is laminated on both main surfaces of the prepreg P1 so that the prepreg P1 is sandwiched between a pair of electrolytic copper foils having a thickness of 12 μm (trade name: HLA-12, manufactured by Nippon Electrolytic Co., Ltd.) A double-sided copper foil-clad laminate was produced by pressing under conditions of a temperature rate of 5 ° C./min, a molding temperature of 230 ° C., a molding pressure of 4 MPa, a molding time of 70 minutes, and a degree of vacuum of 40 hPa.

A conductive pattern circuit having a line width of 50 μm was formed by etching on one main surface of the double-sided copper foil-clad laminate. At this time, on the surface parallel to the main surface, conduction is performed so that the angle formed by the direction in which one glass fiber is arranged (first direction) and the longitudinal direction of the conduction pattern circuit (conduction direction) is 30 degrees. A pattern circuit was formed (the angle between the direction in which the other glass fibers are arranged and the longitudinal direction of the conductive pattern circuit is 60 degrees). On the surface opposite to the surface on which the conductive pattern circuit was manufactured, the entire surface was subjected to etching treatment to remove the copper foil, and a substrate material having a conductive pattern circuit on one main surface was manufactured. An evaluation substrate was produced in the same manner as in Reference Example 1 using this substrate material.

( Reference Examples 8 to 10)
An evaluation board was obtained in the same manner as in Reference Example 7 except that prepregs P2 to P4 were used instead of prepreg P1 and resin films F2 to 4 were used instead of resin film F1.

(Comparative Examples 1-4)
On one main surface of the double-sided copper foil-clad laminate, in the plane parallel to the main surface, the direction in which one glass fiber 76 is arranged (direction A in FIG. 3) and the longitudinal direction of the conductive pattern circuit (conduction direction) An evaluation board was fabricated in the same manner as in Reference Examples 1 to 4 except that the conductive pattern circuit was formed so that the angle formed by (θ _{1 in} FIG. 3) was 90 degrees.

(Evaluation of bendability)
Using an MIT testing machine (trade name: 2101101-00, manufactured by Toyo Seiki Seisakusho), the bendability of the evaluation substrates of Reference Examples 1-4, 7-10, Examples 5, 6 and Comparative Examples 1-4 was evaluated. . The angle θ ₁ (θ in FIG. 1 or FIG. 3) formed by the bending direction (B direction in FIGS. 1 and 3) and the arrangement direction of one glass fiber (fiber 6 in FIG. 1, fiber 76 in FIG. 3) in this evaluation test. ₁ ), and an angle θ ₂ (θ _{2 in} FIG. 1, not shown _in FIG. 3) formed by the bending direction and the arrangement direction of the other glass fiber (fiber 8 in FIG. 1, fiber 78 _in FIG. 3) are: As shown in Tables 1 and 2. The bending direction is the same as the longitudinal direction of the conductive pattern circuit. Under the conditions of a weight of 500 g, a bending angle of 135 degrees, and a speed of 175 cpm with respect to a bending radius of 0.38 mm or 1.00 mm, the number of times of bending until the conductive pattern circuit was disconnected and the number of times until the evaluation substrate was broken were measured. Note that the presence or absence of breakage was determined visually. The results are shown in Tables 1 and 2.

(Evaluation of resistance to twisting)
The resistance against twisting of the evaluation substrates of Reference Examples 1 to 4, 7 to 10, Examples 5 and 6, and Comparative Examples 1 to 4 was evaluated. In this evaluation test, the end of one non-bent part of the evaluation substrate is fixed so that the longitudinal direction of the conductive pattern circuit and the axial direction of the twist are parallel, and 500 g of the other non-bent part is fixed. The number of times until the fiber base material was broken at a twist angle of + 135 ° to −135 ° in a state where a load was applied was evaluated. Note that the presence or absence of breakage was determined visually. The results are shown in Tables 1 and 2.

It is a top view which shows suitable embodiment of the printed wiring board of this invention. It is a side view of the printed wiring board bent. It is a top view of the printed wiring board by which it is bent conventionally.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 2 ... Fiber base material layer, 4 ... Conductor, 6 ... 1st fiber, 8 ... 2nd fiber, 20 ... Non-bending part, 40 ... Bending part, 100,300 ... Printed wiring board.

Claims (3)

A printed wiring board that is bent in a predetermined bending direction,
A fiber substrate containing first fibers arranged in a first direction and second fibers arranged in a second direction intersecting the first direction, and a conductor formed on the fiber substrate A layer, and
The first fibers are arranged so that an angle between the first direction and the bending direction is 30 to 60 degrees ,
The second fibers are arranged so that an angle formed between the second direction and the bending direction is 30 to 60 degrees,
The fiber is a glass cloth, and the thickness of the fiber substrate is 50 μm or less,
The printed wiring board , wherein the fiber base material is impregnated with a thermosetting resin, and the thermosetting resin contains a polyamideimide resin having a siloxane bond . The printed wiring board according to claim 1 , wherein the thermosetting resin contains a resin having a glycidyl group. Bent in a predetermined said bending direction, the electronic device comprising a printed wiring board according to claim 1 or 2.

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