JP4378628B2 - Prepreg, laminated board and printed circuit board using them - Google Patents

Description

  The present invention relates to a prepreg, a laminate, and a printed circuit board using these.

  The laminate for a printed wiring board is obtained by stacking a predetermined number of prepregs each having an electrically insulating resin composition as a matrix and then heating and pressing to integrate them. 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, a thermosetting resin such as a phenol resin, an epoxy resin, a polyimide resin, or a bismaleimide-triazine resin is widely used, and a thermoplastic resin such as a fluorine resin or a polyphenylene ether resin is used. There is also.

  On the other hand, with the spread of information terminal devices such as personal computers and mobile phones, printed circuit boards mounted on them are becoming smaller and higher in density. 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.

  In addition, lead-free solder has progressed from the viewpoint of environmental problems, the melting temperature of solder has increased, and higher heat resistance is required for the substrate, and the demand for halogen-free materials has also increased and bromine-based difficulty has increased. The use of flame retardants has become difficult. In addition, there is a case where so-called repairability is required to remove the chip once mounted, but since this is subject to the same level of heat as chip mounting, the substrate is then chip mounted again. In addition, heat treatment will be added. Along with this, a substrate requiring repairability is also required to have a cyclic thermal shock resistance at a high temperature, and in a conventional insulating resin system, peeling may occur between the fiber base material and the resin.

  A prepreg in which a fiber base material is impregnated with a resin composition containing polyamideimide as an essential component has been proposed in order to have excellent thermal shock resistance, reflow resistance, and crack resistance and to improve fine wiring formation (for example, Patent Document 1). See).

Furthermore, with the miniaturization and high performance of electronic devices, it has become necessary to accommodate printed circuit boards with component mounting in a limited space. In this method, a plurality of printed circuit boards are arranged in multiple stages and connected to each other by a wire harness or a flexible wiring board. In addition, a rigid-flex substrate in which a flexible substrate based on polyimide and a conventional rigid substrate are multilayered is used.
JP 2003-55486 A

  The present invention eliminates the above-mentioned problems of the prior art, impregnates a thin fiber base material with a highly flexible resin excellent in adhesion to metal foil and fiber base material and excellent in heat resistance. Provided are a printed circuit board that is excellent in fillability, dimensional stability, and heat resistance, can be bent when used as a printed circuit board, and can be stored in a casing of an electronic device at high density, and a prepreg and a laminated board that provide the printed circuit board. To do.

The present invention relates to the following.
(1) A prepreg obtained by impregnating a fiber base material with a resin composition containing a resin obtained by reacting a polyamideimide resin and a monoglycidyl compound.
(2) The term (resin) obtained by reacting a polyamideimide resin with a monoglycidyl compound is a resin obtained by reacting 1 to 95 mol% of a monoglycidyl compound with respect to the amide group of the polyamideimide resin ( The prepreg as described in 1).
(3) The prepreg according to item (1) or (2), wherein the polyamideimide resin is a polyamideimide resin having a structure of the general formula (1).

（４）ポリアミドイミド樹脂が、一般式（２）の構造を有するポリアミドイミド樹脂である項（１）乃至（３）のいずれかに記載のプリプレグ。

(4) The prepreg according to any one of Items (1) to (3), wherein the polyamideimide resin is a polyamideimide resin having a structure of the general formula (2).

（ここでＲ_１，Ｒ_２は２価のアルキル基、Ｒ_３，Ｒ_４，Ｒ_７，Ｒ_８は１価のアルキル基又は置換基を有するアルキル基、Ｒ_５，Ｒ_６は１価の芳香族基又は置換基を有する芳香族基を示し、ｍ、ｎはそれぞれ０から４０の整数で１≦ｎ＋ｍ≦５０である）
（５）ポリアミドイミド樹脂が、一般式（１ｃ）で表されるジアミン、一般式（１ａ）または一般式（１ｂ）で表される芳香族環を２個以上有するジアミン及びシロキサンジアミンの混合物と無水トリメリット酸を反応させて得られるジイミドジカルボン酸を含む混合物とジイソシアネート化合物を反応させて得られるポリアミドイミド樹脂である項（１）乃至（４）のいずれかに記載のプリプレグ。

(Where R ₁ and R ₂ are divalent alkyl groups, R ₃ , R ₄ , R ₇ and R ₈ are monovalent alkyl groups or alkyl groups having a substituent, and R ₅ and R ₆ are monovalent aromatic groups. An aromatic group having an aromatic group or a substituent, and m and n are each an integer of 0 to 40, and 1 ≦ n + m ≦ 50)
(5) Polyamideimide resin is a diamine represented by general formula (1c), a mixture of diamine having two or more aromatic rings represented by general formula (1a) or general formula (1b), and siloxane diamine, and anhydrous The prepreg according to any one of Items (1) to (4), which is a polyamideimide resin obtained by reacting a mixture containing diimidedicarboxylic acid obtained by reacting trimellitic acid with a diisocyanate compound.

（式中、Ｘは炭素数１〜３の脂肪族炭化水素基、炭素数１〜３のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基、カルボニル基、単結合又は下記一般式（２ａ）又は（２ｂ）で表される２価の基、Ｙは炭素数１〜３の脂肪族炭化水素基、炭素数１〜３のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基、カルボニル基を示し、Ｒ^１、Ｒ^２、Ｒ^３はそれぞれ独立もしくは同一で水素原子、水酸基、メトキシ基、メチル基、ハロゲン化メチル基を示す。

(Wherein X is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group, a carbonyl group, a single bond, or the following general formula (2a) Or a divalent group represented by (2b), Y is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group, or a carbonyl group. R ¹ , R ² and R ³ are independent or the same and represent a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl group.

但し、Ｚは、炭素数１〜３の脂肪族炭化水素基、炭素数１〜３のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基、カルボニル基又は単結合である。）
（６）樹脂組成物が、熱硬化性樹脂を含む樹脂組成物である項（１）乃至（５）のいずれかに記載のプリプレグ。
（７）熱硬化性樹脂が、２個以上のグリシジル基を持つエポキシ樹脂であり、かつ樹脂組成物が、硬化促進剤または硬化剤を含有する樹脂組成物である項（６）に記載のプリプレグ。
（８）繊維基材が、厚さ５〜１００μｍのガラスクロスである項（１）乃至（７）のいずれかに記載のプリプレグ。
（９）項（１）乃至（８）のいずれかに記載のプリプレグを加熱加圧してなる積層板。
（１０）項（９）に記載の積層板に回路形成を施して得られる印刷回路板。

However, Z is a C1-C3 aliphatic hydrocarbon group, a C1-C3 halogenated aliphatic hydrocarbon group, a sulfonyl group, an ether group, a carbonyl group, or a single bond. )
(6) The prepreg according to any one of Items (1) to (5), wherein the resin composition is a resin composition containing a thermosetting resin.
(7) The prepreg according to item (6), wherein the thermosetting resin is an epoxy resin having two or more glycidyl groups, and the resin composition is a resin composition containing a curing accelerator or a curing agent. .
(8) The prepreg according to any one of Items (1) to (7), wherein the fiber base material is a glass cloth having a thickness of 5 to 100 μm.
(9) A laminate obtained by heating and pressing the prepreg according to any one of items (1) to (8).
(10) A printed circuit board obtained by forming a circuit on the laminate according to item (9).

  The laminated board and printed circuit board obtained by the prepreg in the present invention can be arbitrarily bent, and are excellent in circuit filling property, dimensional stability, heat resistance, and PCT resistance.

  In the present invention, a resin obtained by reacting a polyamideimide resin and a monoglycidyl compound in advance is used. The monoglycidyl compound reacts with the amide group of the polyamideimide resin, thereby reducing the interaction based on the hydrogen bond between the amide groups, thereby reducing the viscosity of the polyamideimide resin. Thereby, the resin flow amount of the prepreg of the present invention using the resin is increased, and the circuit filling property of the prepreg is improved. The monoglycidyl compound used in the present invention is not particularly limited, but a bulky molecular structure is effective for reducing the viscosity. As the monoglycidyl compound, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, n-butyl glycidyl ether and those commercially available as reactive diluents for epoxy resins can be used.

  It is possible to reduce the melt viscosity of the resin and the viscosity of the varnish by reacting these monoglycidyl compounds with the polyamideimide resin. The amount of the monoglycidyl compound to be reacted is preferably 100 mol% or less, more preferably 1 to 95 mol%, particularly preferably 20 to 80 mol%, based on the amide group of the polyamideimide resin. When the amount exceeds 100 mol%, the prepreg produced is sticky, and when it exceeds 95 mol%, the amide group that reacts with the epoxy resin decreases when the epoxy resin is blended, and the curability decreases as a thermosetting resin. In addition, the heat resistance is reduced by the unreacted monoglycidyl compound. If it is less than 1 mol%, the effect of decreasing the viscosity will be insufficient.

  The reaction between the polyamideimide resin and the monoglycidyl compound is carried out in solution. When the polyamideimide resin is varnish, a predetermined amount of monoglycidyl compound is added and reacted at 50 to 200 ° C, preferably 80 to 150 ° C. Although reaction time is not specifically limited, It is preferable to make it react for 1 hour or more. As the reaction proceeds, the viscosity of the polyamideimide resin varnish decreases.

  The polyamideimide resin used in the present invention preferably has the structure of the general formula (1) or the general formula (2). Moreover, the polyamideimide resin used in the present invention may have both the structures of the general formula (1) and the general formula (2). The polyamideimide resin having the general formula (1) structure can be synthesized by using wandamine (trade name, manufactured by Shin Nippon Chemical Co., Ltd.) which is a diamine. The polyamideimide resin having the structure of the general formula (2) can be synthesized using siloxane diamine.

  These polyamideimide resins include a diamine represented by the general formula (1c), a diamine (aromatic diamine) having two or more aromatic rings represented by the general formula (1a) or the general formula (1b), and It is preferably obtained by reacting a mixture containing diimide dicarboxylic acid obtained by reacting a mixture of siloxane diamine and trimellitic anhydride with an aromatic diisocyanate. Further, the polyamideimide resin used in the present invention is a mixture of a diamine (aromatic diamine) having two or more aromatic rings represented by the general formula (1a) or the general formula (1b) and a siloxane diamine and anhydrous. A polyamideimide resin obtained by reacting a mixture containing diimidedicarboxylic acid obtained by reacting trimellitic acid with an aromatic diisocyanate may also be used. Examples of the diamine represented by the general formula (1c) include Wandamine (trade name, manufactured by Shin Nippon Rika Co., Ltd.).

  Furthermore, the polyamideimide resin has a mixing ratio of the diamine a represented by the general formula (1c), a diamine having two or more aromatic rings other than that (aromatic diamine), and a total mole b of siloxane diamine. A / b = 0.1 / 99.9 to 99.9 / 0.1 (molar ratio), more preferably a / b = 10/90 to 50/50, a / b = It is much more preferable that it is 20 / 80-40 / 60.

  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 (trif Oromethyl) 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, Examples include (3,3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether, and the like.

  Examples of the siloxane diamine used in the present invention include the following general formulas (3) to (6).

  In addition, as a siloxane diamine represented by the said General formula (3), X-22-161AS (amine equivalent 450), X-22-161A (amine equivalent 900), X-22-161B (amine equivalent 1500) ( As mentioned above, Shin-Etsu Chemical Co., Ltd. product name), BY16-853 (amine equivalent 650), BY16-853B (amine equivalent 2200), (product name manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like can be exemplified. As the siloxane diamine represented by the general formula (6), X-22-9409 (amine equivalent 700), X-22-1660B-3 (amine equivalent 2200) (above, trade name manufactured by Shin-Etsu Chemical Co., Ltd.) Etc. can be illustrated. Examples of the siloxane diamine include reactive silicon oil KF8010 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 430).

  For the synthesis of the polyamideimide resin of the present invention, a compound represented by the following general formula (7) can be used as the aliphatic diamine.

（但し、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、Ｒ^１及びＲ^２はそれぞれ水素原子、アルキル基、フェニル基また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; Indicates an integer.)

Specific examples of R ¹ and R ² are preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, and a substituted phenyl group. The substituent that may be bonded to the phenyl group is 1 carbon atom. -3 alkyl groups, halogen atoms and the like can be exemplified.

  In the aliphatic diamine, X in the general formula (7) 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), Jeffamine D-2000 (Amine Equivalent 1000), etc. (trade name, manufactured by Sun Techno Chemical Co., Ltd.).

  As the diisocyanate compound used in the method for producing the polyamideimide of the present invention, a compound represented by the following general formula (8) is preferably used.

In the general formula (8), D is a divalent organic group having at least one aromatic ring or a divalent aliphatic hydrocarbon group, and —C ₆ H ₄ —CH ₂ —C ₆ H ₄ — And at least one group selected from the group consisting of a tolylene group, a naphthylene group, a hexamethylene group, a 2,2,4-trimethylhexamethylene group and an isophorone group.

  As the diisocyanate compound represented by the general formula (8), an aliphatic diisocyanate or an aromatic diisocyanate can be used, but it is preferable to use an aromatic diisocyanate, and it is particularly preferable to use both in combination.

  Examples of aromatic diisocyanates include 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, and 2,4-tolylene dimer. As an example, it is particularly preferable to use MDI. By using MDI as the aromatic diisocyanate, the flexibility of the resulting polyamideimide can be improved.

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

  When using an aromatic diisocyanate and an aliphatic diisocyanate in combination, it is preferable to add the aliphatic diisocyanate to about 5 to 10 mol% with respect to the aromatic diisocyanate, and this combination further improves the heat resistance of the resulting polyamideimide resin. Can be made.

  Examples of the thermosetting resin used in the present invention include epoxy resins, polyimide resins, unsaturated polyester resins, polyurethane resins, bismaleimide resins, triazine-bismaleimide resins, phenol resins, and the like. It is preferable to use 1 to 200 parts by weight of a thermosetting resin. In the present invention, using an epoxy resin as a thermosetting resin can be cured at a temperature of 180 ° C. or less, and reacts with an amide group of a polyamide-imide resin to improve thermal, mechanical, and electrical characteristics. Therefore, an epoxy resin having two or more glycidyl groups and a curing agent thereof, an epoxy resin having two or more glycidyl groups and its curing accelerator, or an epoxy resin having two or more glycidyl groups and a curing agent, curing acceleration It is more preferable to use an agent. Further, the more glycidyl groups, the better. The blending amount varies depending on the number of glycidyl groups, and the blending amount may be smaller as the glycidyl group is larger.

  In the present invention, it is preferable to use 1 to 200 parts by weight of a thermosetting resin with respect to 100 parts by weight of the polyamideimide resin. However, if it is less than 1 part by weight, the solvent resistance is inferior. The curable resin is not preferable because Tg is lowered and heat resistance becomes insufficient or flexibility is lowered. Therefore, 3-100 weight part of thermosetting resins are more preferable with respect to 100 weight part of polyamideimide resin, and 10-60 weight part is especially more preferable.

  Epoxy resins include polyglycidyl ethers and phthalic acids obtained by reacting polychlorophenols such as bisphenol A, novolak-type phenol resins, ortho-cresol novolac-type phenol resins or polyhydric alcohols such as 1,4-butanediol with epichlorohydrin. And polyglycidyl ester obtained by reacting a polybasic acid such as hexahydrophthalic acid with epichlorohydrin, an N-glycidyl derivative of a compound having an amine, an amide or a heterocyclic nitrogen base, an alicyclic epoxy resin, and the like.

  The curing agent and curing accelerator of the epoxy resin are not limited as long as they react with the epoxy resin or accelerate curing. For example, amines, imidazoles, polyfunctional phenols, acid anhydrides, etc. Can be used. As the amines, dicyandiamide, diaminodiphenylmethane, guanylurea and the like can be used. As the polyfunctional phenols, hydroquinone, resorcinol, bisphenol A and their halogen compounds, and a novolac type phenol resin which is a condensate with formaldehyde, a resol type A phenol resin can be used, and phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic acid and the like can be used as acid anhydrides. As the curing accelerator, alkyl group-substituted imidazole, benzimidazole and the like can be used as imidazoles.

  In the case of amines, the necessary amounts of these curing agents or curing accelerators are preferably such that the equivalent of the active hydrogen of the amine is approximately equal to the epoxy equivalent of the epoxy resin. In the case of imidazole, which is a curing accelerator, it is not simply an equivalent ratio with active hydrogen, but is empirically required to be 0.001 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin. In the case of polyfunctional phenols and acid anhydrides, 0.6 to 1.2 equivalents of phenolic hydroxyl groups and carboxyl groups are required for 1 equivalent of epoxy resin. If the amount of these curing agents or accelerators is small, uncured epoxy resin remains, and Tg (glass transition temperature) is low. If too large, unreacted curing agent and curing accelerator remain, and insulating properties are maintained. Decreases. The epoxy equivalent of the epoxy resin is preferably taken into account because it can also react with the amide group of the polyamideimide resin.

  In the present invention, a prepreg can be prepared by impregnating and drying a varnish obtained by mixing, dissolving and dispersing a resin composition for prepreg in an organic solvent. Such an organic solvent is not limited as long as solubility is obtained, and examples thereof include dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, and cyclohexanone. It is done.

  A resin composition for obtaining a prepreg is a resin composition containing 100 parts by weight of a polyamideimide resin having the structure of the general formula (1) or the general formula (2) and 1 to 200 parts by weight of a thermosetting resin. It is preferable that the volatilization rate of the varnish solvent is high, and the residual solvent content can be reduced to 5% by weight or less even at a low temperature of 150 ° C. or lower which does not promote the curing reaction of the thermosetting resin. And a laminated board with favorable adhesiveness with copper foil can be obtained.

  In the present invention, a fiber base material is impregnated with a varnish of a resin composition and dried to produce a prepreg. Although it will not restrict | limit especially if it is used when manufacturing a metal foil tension laminated board and a multilayer printed circuit board as a fiber base material, Usually fiber base materials, such as a woven fabric and a nonwoven fabric, are 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 There are organic fibers such as sulfone, carbon, cellulose and the like and mixed papers thereof, and glass fiber woven fabrics are particularly preferably used. As a fiber base material used for a prepreg, it is preferable that thickness is 5-100 micrometers, and 5-50 micrometers is more preferable. A glass cloth having a thickness of 5 to 100 μm is particularly preferably used. By using a glass cloth having a thickness of 5 to 100 μm, it is possible to obtain a printed circuit board that can be bent arbitrarily, and it is possible to reduce dimensional changes associated with temperature, moisture absorption, and the like in the manufacturing process.

  The production conditions of the prepreg are not particularly limited, but it is preferable that the solvent used for the varnish of the resin composition is volatilized by 80% by weight or more. For this reason, there are no restrictions on the production method, drying conditions, etc., the temperature during drying is 80 ° C. to 180 ° C., and the time is not particularly limited in consideration of the gelling time of the varnish. It is preferable that the varnish resin solid content is 30 to 80% by weight based on the total amount of the solid content and the fiber base material.

  The manufacturing method of an insulating board, a laminated board, or a metal foil tension laminated board is as follows. In the present invention, a metal foil is laminated on one or both sides of the prepreg or a laminate obtained by laminating a plurality of the prepregs, if necessary, and usually at a temperature in the range of 150 to 280 ° C, preferably 180 ° C to 250 ° C, usually 0. An insulating plate, a laminated plate, or a metal foil-clad laminate can be produced by heat and pressure molding at a pressure in the range of 5 to 20 MPa, preferably 1 to 8 MPa. By using a metal foil as a metal foil-clad laminate, circuit processing can be applied to this to obtain a printed circuit board.

  As the metal foil used in the present invention, a copper foil or an aluminum foil is generally used. A metal foil of 5 to 200 μm which is usually used for a laminate can be used, but a copper foil is 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.

  Further, it is possible to make a multilayer by further overlapping the prepreg of the present invention and a copper foil on a printed circuit board on which an inner layer circuit is formed. In the prepreg of the present invention, the fluidity of the polyamideimide resin is improved, and the copper foil surface in which the gap between the inner layer circuits is filled with the prepreg resin and laminated is also smooth.

Examples are described below, but the present invention is not limited to these examples.
(Synthesis Example 1)
DDS (diaminodiphenylsulfone) as a diamine (aromatic diamine) having two or more aromatic rings in a 1-liter separable flask equipped with a 25 ml water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer ) 14.9 g (0.06 mol), reactive silicone oil KF-8010 (trade name, amine equivalent 430, manufactured by Shin-Etsu Chemical Co., Ltd.) as a siloxane diamine, and Jeffamine D2000 as an aliphatic diamine (Trade name, manufactured by Sun Techno Chemical Co., amine equivalent 1000) 72.0 g (0.036 mol), Wandamine (trade name, manufactured by Shin Nippon Chemical Co., Ltd.) 11.3 g (0. 36) as the diamine represented by the general formula (1c). 054 mol), TMA (trimellitic anhydride) 80.7 g (0.42 mol) Were charged NMP (N-methyl-2-pyrrolidone) 613 g as aprotic polar solvent were stirred at 80 ° C. 30 min. Then, 150 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature 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. Then, the solution was returned to room temperature (25 ° C.), 55.1 g (0.22 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate, and reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of polyamideimide resin (resin solid content 29% by weight) was obtained.

(Synthesis Example 2)
DDS (diaminodiphenylsulfone) as a diamine (aromatic diamine) having two or more aromatic rings in a 1-liter separable flask equipped with a 25 ml water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer ) 14.9 g (0.06 mol), reactive silicone oil X-22-161A as a siloxane diamine (trade name, amine equivalent 900, manufactured by Shin-Etsu Chemical Co., Ltd.) 90.0 g (0.05 mol), Jeffer as an aliphatic diamine Min D2000 (trade name, manufactured by Sun Techno Chemical Co., amine equivalent 1000) 72.0 g (0.036 mol), Wandamine (trade name, manufactured by Shin Nippon Rika Co., Ltd.) 11.3 g as the diamine represented by the general formula (1c) ( 0.054 mol), TMA (trimellitic anhydride) 80.7 g (0.42 mo) ) Were charged NMP (N-methyl-2-pyrrolidone) 561 g as aprotic polar solvent were stirred at 80 ° C. 30 min. Then, 150 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature 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, the solution was returned to room temperature (25 ° C.), 60.1 g (0.24 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate, and reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of polyamideimide resin (resin solid content 35% by weight) was obtained.

(Synthesis Example 3)
BAPP (2,2) as a diamine (aromatic diamine) having two or more aromatic rings in a 1-liter separable flask equipped with a 25 ml water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer -Bis [4- (4-aminophenoxy) phenyl] propane) 73.8 g (0.18 mol), reactive silicon oil X-22-1660B-3 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent as siloxane diamine) 2200) 88.0 g (0.02 mol) and TMA (trimellitic anhydride) 80.7 g (0.42 mol) as an aprotic polar solvent were charged with 603 g of NMP (N-methyl-2-pyrrolidone) at 80 ° C. Stir for 30 minutes. Then, 150 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature 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, the solution was returned to room temperature (25 ° C.), 60.1 g (0.24 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate, and reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of polyamideimide resin (resin solid content 31% by weight) was obtained.

Example 1
9.3 g of 2-ethylhexyl glycidyl ether (EHGE) as a monoglycidyl compound as a monoglycidyl compound in 431.5 g of NMP solution of the polyamideimide resin of Synthesis Example 1 (resin solid content 29 wt%): 25 mol% ) And stirred at 100 ° C. for 3 hours under a nitrogen stream. Thereafter, the resin was cooled to room temperature (25 ° C.), and NC3000 (epoxy resin, trade name, manufactured by Nippon Kayaku Co., Ltd.) 67.2 g (dimethylacetamide solution having a resin solid content of 50% by weight), 2-ethyl- After blending 6.7 g of 4-methylimidazole (5% by weight dimethylacetamide solution) and stirring for about 1 hour until the resin became homogeneous, it was allowed to stand at room temperature (25 ° C.) for 24 hours for defoaming. A resin composition varnish was obtained.

(Example 2)
As a monoglycidyl compound, 9.3 g of 2-ethylhexyl glycidyl ether (EHGE) as a monoglycidyl compound (ratio with respect to the amide group of the polyamideimide resin: 25 mol%) ) And stirred at 100 ° C. for 3 hours under a nitrogen stream. Thereafter, the resin was cooled to room temperature (25 ° C.), and NC3000 (epoxy resin, trade name, manufactured by Nippon Kayaku Co., Ltd.) 80.2 g (dimethylacetamide solution having a resin solid content of 50% by weight), 2-ethyl- After blending 8.0 g of 4-methylimidazole (5% by weight dimethylacetamide solution) and stirring for about 1 hour until the resin became homogeneous, it was allowed to stand at room temperature (25 ° C.) for 24 hours for defoaming. A resin composition varnish was obtained.

(Example 3)
As a monoglycidyl compound, 15.0 g of phenylglycidyl ether (PGE) as a monoglycidyl compound (ratio to the amide group of the polyamideimide resin: 50 mol%) was added to 436.9 g of NMP solution of the polyamideimide resin of Synthesis Example 3 (solid content of resin 31% by weight). The mixture was stirred at 100 ° C. for 3 hours under a nitrogen stream. Thereafter, the resin was cooled to room temperature (25 ° C.), and NC3000 (epoxy resin, trade name, manufactured by Nippon Kayaku Co., Ltd.) 75.2 g (dimethylacetamide solution having a resin solid content of 50% by weight), 2-ethyl- After blending 7.5 g of 4-methylimidazole (5% by weight dimethylacetamide solution) and stirring for about 1 hour until the resin became homogeneous, it was allowed to stand at room temperature (25 ° C.) for 24 hours for defoaming. A resin composition varnish was obtained.

(Example 4)
Polyamideimide resin KS6600 (trade name, manufactured by Hitachi Chemical Co., Ltd.) 400.0 g of NMP solution (resin solid content 28% by weight) and monoglycidyl compound 15.0 g of phenylglycidyl ether (PGE) (amide group of polyamideimide resin) The mixture was stirred at 100 ° C. for 3 hours under a nitrogen stream. Thereafter, the resin was cooled to room temperature (25 ° C.) and NC3000 (epoxy resin, trade name, manufactured by Nippon Kayaku Co., Ltd.) as a thermosetting resin 63.4 g (dimethylacetamide solution having a resin solid content of 50% by weight), 2-ethyl- After blending 6.3 g of 4-methylimidazole (5% by weight dimethylacetamide solution) and stirring for about 1 hour until the resin became homogeneous, it was allowed to stand at room temperature (25 ° C.) for 24 hours for defoaming. A resin composition varnish was obtained.

(Comparative Example 1)
270.0 g of NMP solution of polyamideimide resin of Synthesis Example 1 (resin solid content 29% by weight) and 40.0 g of NC3000 (epoxy resin, Nippon Kayaku Co., Ltd. trade name) as a thermosetting resin Dimethylacetamide solution) and 4.0 g of 2-ethyl-4-methylimidazole (5% by weight dimethylacetamide solution) were mixed and stirred for about 1 hour until the resin became homogeneous, and then for 24 hours at room temperature for defoaming. The resin composition varnish was left standing at (25 ° C.).

(Comparative Example 2)
NMP solution of KS6600 (trade name, manufactured by Hitachi Chemical Co., Ltd.) as a polyamide-imide resin and NC3000 (epoxy resin, product name, manufactured by Nippon Kayaku Co., Ltd.) as a thermosetting resin After 40.0 g (dimethylacetamide solution of resin solid weight%) and 4.0 g of 2-ethyl-4-methylimidazole (5 wt% dimethylacetamide solution) were mixed and stirred for about 1 hour until the resin became homogeneous The resin composition varnish was left to stand at room temperature (25 ° C.) for 24 hours for defoaming.

(Preparation of prepreg and double-sided copper-clad laminate)
The resin composition varnishes produced in Examples 1 to 4 and Comparative Examples 1 and 2 were impregnated into a glass cloth having a thickness of 0.028 mm (trade name 1037 manufactured by Asahi Schwer, Inc.), then heated and dried at 150 ° C. for 15 minutes. Thus, a prepreg having a resin content of 70% by weight was obtained. A 12 μm thick electrolytic copper foil (trade name F2-WS-12, manufactured by Furukawa Electric Co., Ltd.) is stacked on both sides of the prepared prepreg so that the adhesive surface is aligned with the prepreg, and a press at 230 ° C. for 90 minutes and 4.0 MPa. A double-sided copper-clad laminate was produced under the conditions. The following evaluation was performed using the produced prepreg and double-sided copper-clad laminate. The results are shown in Table 1.

(Evaluation item)
(1) Copper foil peeling strength The copper foil peeling strength of the obtained double-sided copper-clad laminate was measured.
(2) Solder heat resistance As the solder heat resistance of the double-sided copper-clad laminate, it was immersed in a solder bath at 260 ° C and 288 ° C, and the time until occurrence of abnormality such as blistering and peeling was measured.
(3) Flexibility The flexibility (foldability) of the double-sided copper-clad laminate from which the copper foil was removed by etching was evaluated. ○: No break, ×: Break
(4) Amount of resin flow The prepreg is punched into a circle with a diameter of 10 mm and sandwiched between two release-treated polyimide films (trade names of Upilex 50S Ube Industries Co., Ltd.) and pressed under conditions of 230 ° C., 6 MPa for 5 minutes. went. The deformation amount of the oozing out by the press was measured from the average of the three diameters of the prepreg after the press and evaluated as the resin flow amount.
(5) Circuit filling property A prepreg produced on an inner circuit board on which a comb pattern having lines / spaces of 50 μm / 50 μm, 75 μm / 75 μm, 100 μm / 100 μm, 150 μm / 150 μm, 200 μm / 200 μm is formed, and a thickness of 12 μm Each of the electrolytic copper foils (F2-WS-12 manufactured by Furukawa Electric Co., Ltd.) was overlapped so that the adhesive surfaces were combined with the prepreg, and a multilayer board was produced under a press condition of 230 ° C., 90 minutes, 4.0 MPa. The copper foil was removed by etching, and the resin filling property between the inner layer circuits was observed with a microscope. ○: No gap between inner layer circuits, ×: There is a gap between inner layer circuits.

  The copper foil peel strength was 0.9 to 1.2 kN / m in any combination with the prepregs of Examples 1 to 4. Moreover, as a result of being immersed in the solder bath of 260 degreeC and 288 degreeC and measuring solder heat resistance, abnormality, such as blistering and peeling, was not seen for 5 minutes or more at any temperature. In Examples 1-4, it was rich in flexibility and could be bent arbitrarily. In Examples 1 to 4, the resin flow amount of the prepreg was large, the resin was filled between the comb circuits, and no voids were observed.

On the other hand, in Comparative Example 2, blistering that appeared to be caused by prepreg voids occurred at 288 ° C. for 60 seconds. Moreover, the flexibility was insufficient, and in Comparative Example 2, the base material was broken when it was bent. The resin flow amount of the prepreg was also small, and in Comparative Examples 1 and 2, many voids were observed between the comb circuits.

Claims (10)

  A prepreg obtained by impregnating a fiber substrate with a resin composition containing a resin obtained by reacting a polyamideimide resin and a monoglycidyl compound.   The resin obtained by reacting the polyamideimide resin and the monoglycidyl compound is a resin obtained by reacting 1 to 95 mol% of the monoglycidyl compound with respect to the amide group of the polyamideimide resin. Prepreg. The prepreg according to claim 1 or 2, wherein the polyamideimide resin is a polyamideimide resin having a structure of the general formula (1).

The prepreg according to any one of claims 1 to 3, wherein the polyamideimide resin is a polyamideimide resin having a structure of the general formula (2).

(Where R ₁ and R ₂ are divalent alkyl groups, R ₃ , R ₄ , R ₇ and R ₈ are monovalent alkyl groups or alkyl groups having a substituent, and R ₅ and R ₆ are monovalent aromatic groups. An aromatic group having an aromatic group or a substituent, and m and n are each an integer of 0 to 40, and 1 ≦ n + m ≦ 50) Polyamideimide resin is a diamine represented by general formula (1c), a mixture of diamine having two or more aromatic rings represented by general formula (1a) or general formula (1b), and siloxane diamine, and trimellitic anhydride The prepreg according to any one of claims 1 to 4, which is a polyamide-imide resin obtained by reacting a mixture containing diimide dicarboxylic acid obtained by reacting a diisocyanate with a diisocyanate compound.

(Wherein X is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group, a carbonyl group, a single bond, or the following general formula (2a) Or a divalent group represented by (2b), Y is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group, or a carbonyl group. R ¹ , R ² and R ³ are independent or the same and represent a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl group.

However, Z is a C1-C3 aliphatic hydrocarbon group, a C1-C3 halogenated aliphatic hydrocarbon group, a sulfonyl group, an ether group, a carbonyl group, or a single bond. )   The prepreg according to any one of claims 1 to 5, wherein the resin composition is a resin composition containing a thermosetting resin.   The prepreg according to claim 6, wherein the thermosetting resin is an epoxy resin having two or more glycidyl groups, and the resin composition is a resin composition containing a curing accelerator or a curing agent.   The prepreg according to any one of claims 1 to 7, wherein the fiber base material is a glass cloth having a thickness of 5 to 100 µm.   A laminate obtained by heating and pressing the prepreg according to claim 1. A printed circuit board obtained by forming a circuit on the laminate according to claim 9.