JP2009280727A - Urethane-modified polyimide-based resin composition, paste comprising the same composition, and electronic component formed from the same paste - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a urethane-modified polyimide-based resin composition excellent in (1) solubility in non-nitrogen-based solvents, (2) low-temperature dryability/curability, (3) low warpage, (4) flexibility, and (5) printability, and having excellent heat and chemical resistances, electrical characteristics, workability, and economical efficiency, to provide a polyimide-based resin composition simultaneously satisfying even (6) flame retardancy, and having the excellent heat and chemical resistances, electrical characteristics, workability, and economical efficiency, to provide a paste comprising the composition, and to provide an electronic component having a solder resist layer, a surface protective layer, an interlaminar insulating layer or an adhesive layer obtained from the paste. <P>SOLUTION: The urethane-modified polyimide-based resin composition includes a urethane-modified polyimide-based resin comprising (a) a trivalent and/or a tetravalent polycarboxylic acid derivative having an acid anhydride group, (b) a polyoxyalkylene glycol, (c) a polyalkylene oxide adduct of a bisphenol represented by general formula (1) (wherein, m and n are each an integer of ≥1, and may be same or different; R1 represents a 1-20C alkylene group; and R2 and R3 represent each a hydrogen or a 1-4C alkyl group, and may be the same or different), and (d) an aliphatic polyamine residue derivative as essential components as a component (A), an epoxy resin having ≥2 epoxy groups based on one molecule as a component (B), and an inorganic or an organic filler as a component (C). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is particularly useful for flexible printed wiring board applications, has excellent heat resistance and flexibility, and is a modified polyimide resin composition suitable for coating methods such as a printing press, dispenser or spin coater, a paste comprising the same, And an electronic component having a solder resist layer, a surface protective layer, an interlayer insulating layer, or an adhesive layer obtained therefrom.

  Currently, flexible printed wiring boards are required for electronic equipment components that require flexibility and small space, for example, between device mounting boards for display devices such as liquid crystal displays and plasma displays, and boards such as mobile phones, digital cameras, and portable game machines. Widely used for relay cables, operation switch board, etc.

  By the way, since a solder resist layer, a surface protective layer, an interlayer insulating layer or an adhesive layer, which are constituent elements of a flexible printed wiring board, are often applied and printed in a solution form, as a material thereof, a solvent-soluble ring-closing type Formulations made of polyimide resins have been proposed. However, conventionally, as a solvent for varnishing a polyimide resin, a high-boiling nitrogen polar solvent such as N-methyl-2-pyrrolidone has been used. There was a problem that a curing process was required, and thermal deterioration of the electronic member occurred. In addition, if the varnish is applied to the substrate and then left standing for a long time, ink, whitening of the coating film and voids may occur due to moisture absorption of the high boiling point nitrogen-based solvent, which makes it difficult to set the working conditions. .

  Furthermore, since the polyimide resin is generally hard with a high elastic modulus, when it is laminated on a substrate such as a film or copper foil, a warp or the like is generated due to a difference in elastic modulus, which causes a problem in a subsequent process. In addition, the cured film lacks flexibility and has a problem of poor flexibility.

Examples of the polyimide-based resin that is soluble in a non-nitrogen solvent and has low warpage and flexibility obtained by making the resin flexible and low elastic modulus include (Patent Document 1), (Patent Document 2), etc. A polysiloxane-modified polyimide resin is disclosed.
JP 7-304950 A JP-A-8-333455

  These polysiloxane-modified polyimide resins use a diamine having an expensive dimethylsiloxane bond as a starting material for reducing the elastic modulus, and are inferior in economic efficiency. In addition, as the amount of polysiloxane copolymerized increases, there is a problem that adhesion, solvent resistance, and chemical resistance decrease.

In order to improve these drawbacks, for example, (Patent Literature 3), (Patent Literature 4), (Patent Literature 5) and the like disclose compositions using a polycarbonate-modified polyimide resin.
JP 2001-302895 A JP 2003-138015 A JP 2007-84652 A

  The polycarbonate-modified polyimide resin disclosed herein has improved defects derived from polysiloxane and has good printability, but the paste obtained from this resin is modified with polycarbonate to reduce warpage. It is necessary to increase the amount, and the heat resistance tends to decrease. Furthermore, it is difficult for these pastes to achieve satisfactory performance in reliability tests called HHBT and PCBT. In general, a low elastic modulus component is introduced in order to obtain low warpage. However, in many cases, the flame retardancy is decreased. The paste disclosed here does not provide sufficient flame retardancy.

On the other hand, (Patent Document 6) contains at least one component selected from the group consisting of polyether, polyester, polyacrylonitrile-butadiene copolymer, polycarbonate diol and dimer acid as a copolymer component, and an isophorone residue. (Patent Document 7) discloses a polyimide resin containing a polyether as a copolymer component, trimellitic acid and cyclohexanedicarboxylic acid as an acid component, and a composition comprising the same. Yes. Although the polyimide resin disclosed here is expected to be excellent in solubility in non-nitrogen solvents, it has low warpage, solder heat resistance, and printability as a flexible printed wiring board intended for the present invention. Are not satisfied at the same time. In addition, any polyimide resin remains as a reaction solvent and the varnish stability is low, the resin is likely to precipitate over time, and for the purpose of use, it is further replaced with a low-boiling solvent with high solubility through reprecipitation. Is inferior in economic efficiency. Moreover, the composition disclosed here cannot obtain sufficient heat resistance and flame retardancy.
JP 2003-289594 A Patent No. 3729291

(Patent Document 8) discloses a composition using a polyimide resin containing a polyalkylene oxide adduct of bisphenol A. The polyimide resin composition disclosed herein is excellent in heat resistance, but is not soluble in a non-nitrogen solvent and cannot be said to have low warpage and flexibility. In addition, flame retardancy is not obtained.
JP 11-293218 A

  As can be seen from these examples, the conventional techniques so far have (1) non-nitrogen solvent solubility, (2) low temperature drying / curability, (3) low warpage, (4) flexibility, and (5) printability at the same time. A polyimide resin composition applicable as a solder resist layer, a surface protective layer, an interlayer insulating layer or an adhesive layer, which satisfies all, has not been obtained. Furthermore, (6) a polyimide resin composition applicable as a solder resist layer, a surface protective layer, an interlayer insulating layer or an adhesive layer that simultaneously satisfies flame retardancy has not been obtained. The present invention eliminates the above-mentioned problems of the prior art, and (1) non-nitrogen solvent solubility (2) low temperature drying / curability (3) low warpage (4) flexibility (5) excellent printability Urethane-modified polyimide resin composition with excellent heat resistance, chemical resistance, electrical properties, workability and economy, and (6) flame retardant properties at the same time, heat resistance, chemical resistance, electrical properties, work It is an object of the present invention to provide an electronic component having a polyimide resin composition excellent in properties and economy, a paste comprising them, and a solder resist layer, a surface protective layer, an interlayer insulating layer, or an adhesive layer obtained therefrom.

（式（１）において、ｍ、ｎは１以上の整数であって、同じであっても異なっていてもよく、Ｒ１は炭素数１〜２０のアルキレン基、Ｒ２及びＲ３は水素もしくは炭素数１〜４のアルキル基を示し、互いに同じであっても異なっていてもよい）
（２）
さらに（Ｄ）成分として、ウレタン変性ポリイミド系樹脂に溶解する非ハロゲン系難燃剤を含有する請求項１記載のウレタン変性ポリイミド系樹脂組成物。
（３）
さらに（Ｅ）成分として、硬化促進剤を含有する請求項１又は２記載のウレタン変性ポリイミド系樹脂組成物。
（４）
ウレタン変性ポリイミド系樹脂がエーテル系溶媒、エステル系溶媒、ケトン系溶媒及び芳香族炭化水素系溶媒から選ばれる有機溶媒中で反応させて得られるウレタン変性ポリイミド樹脂であり、かつ溶媒置換をおこなわないため上記以外の溶媒を含有しない、請求項１から３のいずれか一項に記載のウレタン変性ポリイミド系樹脂組成物。
（５）
非ハロゲン系難燃剤がホスファゼン及び／又はホスフィン酸誘導体である請求項２から４のいずれか一項に記載のウレタン変性ポリイミド系樹脂組成物。
（６）
揺変度で１．３以上のチクソトロピー性を有する、請求項１から５のいずれか一項に記載のウレタン変性ポリイミド系樹脂組成物からなるペースト。
（７）
請求項１から６のいずれか一項に記載のウレタン変性ポリイミド系樹脂組成物又はそれからなるペーストを乾燥硬化して得られるソルダーレジスト層、表面保護層、層間絶縁層又は接着層を有する電子部品。 As a result of intensive studies in order to solve the above problems, the present inventors have finally completed the present invention. That is, this invention consists of the following structures.
(1)
As component (A), (a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group, (b) a polyoxyalkylene glycol (c) a polyalkylene of bisphenol represented by the general formula (1) Oxide adduct (d) Urethane-modified polyimide resin (B) component having an aliphatic polyamine residue derivative as an essential component, an epoxy resin having two or more epoxy groups per molecule,
(C) A urethane-modified polyimide resin composition containing an inorganic or organic filler as a component.

(In the formula (1), m and n are integers of 1 or more and may be the same or different, R1 is an alkylene group having 1 to 20 carbon atoms, R2 and R3 are hydrogen or 1 carbon atom. To 4 alkyl groups, which may be the same or different)
(2)
The urethane-modified polyimide resin composition according to claim 1, further comprising a non-halogen flame retardant that dissolves in the urethane-modified polyimide resin as component (D).
(3)
The urethane-modified polyimide resin composition according to claim 1 or 2, further comprising a curing accelerator as component (E).
(4)
The urethane-modified polyimide resin is a urethane-modified polyimide resin obtained by reacting in an organic solvent selected from ether solvents, ester solvents, ketone solvents, and aromatic hydrocarbon solvents, and does not perform solvent substitution. The urethane-modified polyimide resin composition according to any one of claims 1 to 3, which contains no solvent other than the above.
(5)
The urethane-modified polyimide resin composition according to any one of claims 2 to 4, wherein the non-halogen flame retardant is a phosphazene and / or a phosphinic acid derivative.
(6)
The paste which consists of a urethane-modified polyimide resin composition as described in any one of Claim 1 to 5 which has thixotropic property of 1.3 or more by a throttling degree.
(7)
An electronic component having a solder resist layer, a surface protective layer, an interlayer insulating layer or an adhesive layer obtained by drying and curing the urethane-modified polyimide resin composition according to any one of claims 1 to 6 or a paste made thereof.

  According to the present invention, it has been difficult to satisfy simultaneously at the same time (1) Non-nitrogen solvent solubility (2) Low temperature drying / curability (3) Low warpage (4) Flexibility (5) Excellent printability, In addition, a modified polyimide resin composition excellent in heat resistance, chemical resistance, electrical properties, workability and economics, and in addition, (6) flame retardant properties are satisfied at the same time, heat resistance, chemical resistance, electrical properties, It is possible to provide an electronic component having a polyimide resin composition excellent in workability and economy, a paste comprising them, and a solder resist layer, a surface protective layer, an interlayer insulating layer or an adhesive layer obtained therefrom.

  The present invention will be described in detail below. The urethane-modified polyimide resin composition of the present invention and the paste comprising the urethane-modified polyimide resin as component (A), epoxy resin having two or more epoxy groups per molecule as component (B), component (C) As an inorganic or organic filler, as a component (D) a non-halogen flame retardant that dissolves in the component (A), and as a component (E) a curing accelerator.

<Urethane-modified polyimide resin (A) component>
The urethane-modified polyimide resin of component (A) used in the present invention is a method of producing from a polycarboxylic acid component having an acid anhydride group and an isocyanate component (isocyanate method), or a polycarboxylic acid component having an acid anhydride group It is produced by a known method such as a method (direct method) in which an amine is reacted with an amine to form an amic acid, followed by ring closure. Industrially, the isocyanate method is advantageous.

  As the component (a) constituting the urethane-modified polyimide resin used in the present invention, a trivalent and / or tetravalent acid anhydride group that generally reacts with an isocyanate component or an amine component to form a polyimide resin. Polycarboxylic acid derivatives are used.

  Examples of aromatic polycarboxylic acid derivatives include trimellitic anhydride, pyromellitic dianhydride, ethylene glycol bisanhydro trimellitate, propylene glycol bisanhydro trimellitate, 1,4-butanediol bisanhydro. Alkylene glycol bisanhydro trimellitate such as trimellitate, hexamethylene glycol bisanhydro trimellitate, polyethylene glycol bisanhydro trimellitate, polypropylene glycol bisanhydro trimellitate, 3,3 ', 4,4 '-Benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5 8-Naphthalenetetracarboxylic dianhydride 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride , M-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 1,1,1,3,3,3-hexafluoro- 2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 2, 2-bis [4- (2,3- or 3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (2,3- or 3,4-dicarboxyphenoxy) phenyl] propane Examples thereof include dianhydrides and 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride.

  Examples of the aliphatic or alicyclic polycarboxylic acid derivatives include butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, and cyclobutane. Tetracarboxylic dianhydride, hexahydropyromellitic dianhydride, cyclohex-1-ene-2,3,5,6-tetracarboxylic dianhydride, 3-ethylcyclohex-1-ene-3- ( 1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3- Ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1- (1,2), 3,4-tetracarboxylic dianhydride 1-propylcyclohe Sun-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3), 3- (2,3) -tetracarboxylic dianhydride , Dicyclohexyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 1-propylcyclohexane -1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3), 3- (2,3) -tetracarboxylic dianhydride , Dicyclohexyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2 .2] Octane-2,3,5,6-tetracarboxylic dianhydride , Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, hexahydroterephthalic trimellitic anhydride, and the like.

  These trivalent or tetravalent polycarboxylic acid derivatives may be used alone or in combination of two or more. Considering heat resistance, transparency, adhesion, solubility, cost, pyromellitic dianhydride, trimellitic anhydride, ethylene glycol bisanhydro trimellitate, 3, 3 ', 4, 4 '-Benzophenone tetracarboxylic dianhydride and 3,3', 4,4'-biphenyltetracarboxylic dianhydride are preferable, and trimellitic anhydride and ethylene glycol bisanhydro trimellitate are more preferable.

The copolymerization amount of the component (a) is preferably 50 mol% or more and 90 mol% or less, and 65 mol% or more and 80 mol% or less, in a molar ratio with respect to 100 mol% of all polyamine residue derivatives to be reacted. Is more preferable. If it is less than 50 mol%, flame retardancy, mechanical properties, and heat resistance cannot be obtained. If it exceeds 90 mol%, a sufficient amount of the components (b) and (c) described later cannot be copolymerized, and thus low warpage. And solubility in non-nitrogen solvents decreases.
In addition, in the urethane-modified polyimide resin used in the present invention, aliphatic, alicyclic, and aromatic polycarboxylic acids may be further copolymerized as necessary as long as the target performance is not impaired. Examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, eicosanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3 -Methyladipic acid, 3-methylpentanedicarboxylic acid, 2-methyloctanedicarboxylic acid, 3,8-dimethyldecanedicarboxylic acid, 3,7-dimethyldecanedicarboxylic acid, 9,12-dimethyleicosane diacid, fumaric acid, Examples of the alicyclic dicarboxylic acid such as maleic acid, dimer acid, hydrogenated dimer acid, etc. include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4,4′- Examples of aromatic dicarboxylic acids such as dicyclohexyl dicarboxylic acid include isophthalic acid, Refutaru acid, orthophthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, stilbene dicarboxylic acid and the like. These dicarboxylic acids may be used alone or in combination of two or more. In view of heat resistance, adhesion, solubility, cost, etc., sebacic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, and isophthalic acid are preferable.

  The polyoxyalkylene glycols of component (b) constituting the urethane-modified polyimide resin used in the present invention are copolymerized as flexible components that impart flexibility, low warpage, solubility, etc. to the polyimide resin. Is done. By copolymerizing these, the elastic modulus of the resin is lowered, and the solubility (varnish) stability in a non-nitrogen solvent used as a polymerization solvent is increased.

  Examples of polyoxyalkylene glycols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (neopentyl glycol / tetramethylene glycol), and the like. The number average molecular weight is preferably 500 or more and 3000 or less, more preferably 1000 or more and 2000 or less. When the molecular weight is less than 500, the heat resistance, flexibility and low warpage are insufficient, and when it exceeds 3000, the modification reaction does not proceed and the solubility may decrease.

  The copolymerization amount of the component (b) is preferably such that the mass of the polyurethane comprising the component (b) and the polyamine residue derivative is 15% by mass to 60% by mass of the urethane-modified polyimide resin, and 20% by mass. As mentioned above, it is still more preferable to set it as 35 mass% or less. If it is less than 15% by mass, the elastic modulus does not sufficiently decrease, and warping occurs when laminated, and the solubility in non-nitrogen solvents decreases, so that the resin precipitates within one month at 5 ° C. to 30 ° C. There is a risk of coming. This is particularly noticeable when γ-butyrolactone, glymes and cyclohexanone, which are preferably used in the present invention, are used as a solvent. On the other hand, if it exceeds 60% by mass, flame retardancy, mechanical properties, and heat resistance may deteriorate.

  In the present invention, in addition to the polyoxyalkylene glycols, other flexible components may be copolymerized as necessary within the range not impairing the intended performance. For example, aliphatic / aromatic polyester diols (trade name VYLON220, manufactured by Toyobo Co., Ltd.), aliphatic / aromatic polycarbonate diols (trade name PLACEL-CD220, manufactured by Daicel Chemical Industries, Ltd., Kuraray Co., Ltd.) Manufactured, trade name C-2015N, etc.), polycaprolactone diols (produced by Daicel Chemical Industries, trade name PLACEL-220, etc.), carboxy-modified acrylonitrile butadiene rubbers (produced by Ube Industries, trade name Hypro CTBN 1300 × 13) And the like, and polysiloxane derivatives such as polydimethylsiloxane diol, polymethylphenylsiloxane diol, and carboxy-modified polydimethylsiloxanes.

The polyalkylene oxide adduct of bisphenol represented by the general formula (1) of the component (c) constituting the urethane-modified polyimide resin used in the present invention has a non-nitrogen-based solvent solubility, is acceptable in the modified polyimide resin. Copolymerized as a component that imparts flexibility. Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, and polytetramethylene oxide. Preferably, those having a number average molecular weight of 200 or more and 2000 or less are used.
Specifically, polyethylene oxide adduct of bisphenol A (manufactured by Sanyo Chemical Industries, trade name Newpol BPE series), polypropylene oxide adduct of bisphenol A (manufactured by Sanyo Chemical Industries, trade name Newpol BP) Series).

  The copolymerization amount of the component (c) is preferably such that the mass of the polyurethane comprising the component (c) and the polyamine residue derivative is 15% by mass or more and 45% by mass or less of the urethane-modified polyimide resin, and is 20% by mass. As mentioned above, it is still more preferable to set it as 35 mass% or less. If it is less than 15% by mass, the solubility in a non-nitrogen solvent is lowered, so that the resin may be precipitated within one month at 5 ° C. to 30 ° C. This is particularly noticeable when γ-butyrolactone, glymes and cyclohexanone, which are preferably used in the present invention, are used as a solvent. On the other hand, if it exceeds 45% by mass, flame retardancy, mechanical properties, and heat resistance may deteriorate.

  As the component (d) constituting the urethane-modified polyimide resin used in the present invention, polyisocyanate and polyamine which are aliphatic polyamine residue derivatives are used. The aliphatic polyamine residue imparts low warpage to the urethane-modified polyimide resin. Specific examples of the polyisocyanate include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. Hexamethylene diisocyanate is preferred.

  In the urethane-modified polyimide resin used in the present invention, in addition to the aliphatic polyamine residue derivative, the alicyclic polyamine residue derivative is further added as necessary as long as the low warpage, heat resistance and flame retardancy are not impaired. May be copolymerized. Specific examples of the polyisocyanate include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, transcyclohexane-1,4-diisocyanate, and hydrogenated m-xylylene diisocyanate. In view of heat resistance, adhesion, solubility, cost, etc., isophorone diisocyanate and 4,4′-dicyclohexylmethane diisocyanate are preferable.

  In the urethane-modified polyimide resin used in the present invention, in addition to the aliphatic polyamine residue derivative, an aromatic polyamine residue derivative is further added to improve non-nitrogen solvent solubility, heat resistance, and flame retardancy. Polymerization is preferred.

  Specifically, for polyisocyanates, for example, diphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5 , 3'- or 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- Or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane -3,3'-diisocyanate Diphenylmethane-3,4'-diisocyanate, diphenylether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2, 6-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4 '-[2,2bis (4-phenoxyphenyl) propane] diisocyanate, 3,3' or 2 2,2′-dimethylbiphenyl-4,4′-diisocyanate, 3,3′- or 2,2′-diethylbiphenyl-4,4′-diisocyanate, 3,3′-dimethoxybiphenyl-4,4′-diisocyanate, 3,3'-dietoki Biphenyl-4,4'-diisocyanate, and the like. Considering heat resistance, adhesion, solubility, cost, etc., diphenylmethane-4,4'-diisocyanate, tolylene-2,4-diisocyanate, m-xylylene diisocyanate, 3,3 'or 2,2'- Dimethylbiphenyl-4,4′-diisocyanate is preferable, and diphenylmethane-4,4′-diisocyanate and tolylene-2,4-diisocyanate are more preferable.

  The molar ratio of the aliphatic polyamine residue derivative of component (d) to 100 mol% of all polyamine residue derivatives is preferably 40 mol% or more and 90 mol% or less, and 45 mol% or more and 75 mol% or less. Is more preferable. If the amount is less than 40 mol%, sufficient low warpage cannot be obtained. If the amount is more than 90 mol%, the solubility in a non-nitrogen solvent decreases, so that the resin may solidify within 5 months at 30 ° C to 30 ° C. is there. This is particularly noticeable when γ-butyrolactone, glymes and cyclohexanone, which are preferably used in the present invention, are used as a solvent. In addition, flame retardancy, mechanical properties, and heat resistance may be reduced.

  Further, a polyamine residue derivative having three or more functional groups may be used, and a polyamine residue derivative stabilized with a blocking agent necessary for avoiding changes over time may be used. In the case of polyisocyanate, the blocking agent includes alcohol, phenol, oxime, etc., but is not particularly limited. These polyisocyanates may be used alone or in combination of two or more. When the polymerization is carried out with an excess of isocyanate, the isocyanate group at the end of the resin can be blocked with a blocking agent such as alcohols, lactams or oximes after completion of the polymerization.

  In the case of the isocyanate method, the (a) component trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group, the (b) component polyoxyalkylene glycol, and the (c) component general formula (1) The polyisocyanate adduct of bisphenol A and the amount of polyisocyanate that gives all polyamine residues are represented by the number of acid anhydride groups, the number of carboxylic acid groups, and the ratio of the number of hydroxyl groups to the number of isocyanate groups: number of isocyanate groups / number of acid anhydride groups. It is preferable that + carboxylic acid group number + hydroxyl group number = 0.80 to 1.20. If it is less than 0.8 or exceeds 1.20, it will be difficult to increase the molecular weight of the urethane-modified polyimide resin, heat resistance and flexibility may be lowered, and the coating film may be brittle.

  The polymerization reaction of the urethane-modified polyimide resin used in the present invention is preferably free in the presence of an organic solvent selected from ether solvents, ester solvents, ketone solvents and aromatic hydrocarbon solvents, for example, in the isocyanate method. It is carried out by heat condensation while removing the generated carbon dioxide gas from the reaction system.

  Examples of the solvent include ether solvents such as diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether (ethyl diglyme), triethylene glycol dimethyl ether (triglyme), and triethylene glycol diethyl ether (ethyl triglyme). Examples of ketone solvents such as methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, and the like, and aromatic hydrocarbon solvents such as toluene, xylene, and solvesso. These may be used alone or in combination of two or more.

  When producing the urethane-modified polyimide resin used in the present invention, it is preferable to select and use a solvent that dissolves the urethane-modified polyimide resin to be produced, and is suitable as a solvent for the composition and paste as it is after polymerization. More preferably, one is used. In this case, complicated operations such as solvent replacement are eliminated, and it becomes possible to manufacture at low cost. The boiling point is preferably 140 ° C or higher and 230 ° C or lower. When the temperature is lower than 140 ° C., the solvent may be volatilized during the polymerization reaction. In addition, when screen printing is performed, for example, the solvent volatilization may quickly cause clogging. When it exceeds 230 ° C., it becomes difficult to impart low temperature drying / curing properties. Γ-butyrolactone, cyclohexanone, diglyme, and triglyme are preferred for relatively high volatility, imparting low temperature drying / curing properties, excellent varnish stability, and conducting reaction in a homogeneous system efficiently.

  The amount of the solvent used is preferably 0.8 to 5.0 times (mass ratio) of the urethane-modified polyimide resin to be generated, and more preferably 0.9 to 2.0 times. If it is less than 0.8 times, the viscosity at the time of synthesis is too high, and the synthesis tends to be difficult due to the inability to stir. If it exceeds 5.0 times, the reaction rate tends to decrease.

  In the case of the isocyanate method, the reaction temperature is preferably 60 to 200 ° C, more preferably 100 to 180 ° C. If it is less than 60 ° C., the reaction time becomes too long, and if it exceeds 200 ° C., the monomer component may be decomposed during the reaction. In addition, a three-dimensional reaction occurs and gelation is likely to occur. The reaction temperature may be performed in multiple stages. The reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions employed, particularly the reaction concentration.

  In the case of the isocyanate method, triethylamine, lutidine, picoline, undecene, triethylenediamine (1,4-diazabicyclo [2.2.2] octane), DBU (1,8-diazabicyclo [5.4.0] are used to accelerate the reaction. ] -7-undecene) and the like, lithium methylate, sodium methylate, sodium ethylate, alkali metal such as potassium butoxide, potassium fluoride, sodium fluoride, alkaline earth metal compound or titanium, cobalt, You may carry out in presence of catalysts, such as metals, such as tin, zinc, and aluminum, and a metalloid compound.

  As the method for producing the urethane-modified polyimide resin used in the present invention, in the case of the isocyanate method, for example, (1) (a) component, (b) component, (c) component and (d) component are used at a time. And (2) the component (a) and / or the component (b) and / or the component (c) and an excess amount of the component (d) to react with each other. After synthesizing a modified imide oligomer having an isocyanate group, (a) component and / or (b) component and / or (c) component are added and reacted to obtain a urethane-modified polyimide resin, (3) excess (A) component and / or (b) component and / or (c) component and (d) component are reacted to form a urethane having a carboxylic acid group and / or an acid anhydride group and / or a hydroxyl group at the terminal Modified imide oligomer After combining, the method, and the like to obtain a urethane-modified polyimide resin were reacted to add the component (d).

  The logarithmic viscosity of the urethane-modified polyimide resin used in the present invention is preferably from 0.1 dl / g to 2.0 dl / g, and more preferably from 0.2 dl / g to 1.8 dl / g. When the logarithmic viscosity is 0.1 dl / g or less, the heat resistance may be lowered or the coating film may be brittle. In addition, the tackiness of the paste is strong and the separation of the plate is poor. On the other hand, at 2.0 dl / g or more, it becomes difficult to dissolve in a solvent, and it tends to become insoluble during polymerization. In addition, the viscosity of the varnish becomes high and handling becomes difficult, and the adhesion to the base material decreases. Furthermore, the nonvolatile content concentration of the paste cannot be increased, and it becomes difficult to form a thick film. A urethane-modified polyimide resin in this range can be obtained by appropriately adjusting the polymerization conditions such as the monomer ratio and the polymerization temperature.

  The glass transition temperature of the urethane-modified polyimide resin used in the present invention is preferably 20 ° C. or higher, more preferably 60 ° C. or higher. Below 20 ° C., the heat resistance is insufficient and the resin may block. Although an upper limit is not specifically limited, 300 degrees C or less is preferable from a solvent solubility viewpoint. A urethane-modified polyimide resin in this range can be obtained by appropriately adjusting the polymerization conditions such as the monomer ratio.

<Epoxy resin (B) component>
Examples of the epoxy resin of component (B) used in the present invention include bisphenol A type epoxy resins such as trade names jER828 and 1001 manufactured by Japan Epoxy Resin Co., Ltd., and trade names ST-2004 manufactured by Toto Kasei Co., Ltd. Hydrogenated bisphenol A type epoxy resins such as 2007, trade name YDF-170, manufactured by Toto Kasei Co., Ltd., bisphenol F type epoxy resins such as 2004, product names YDB-400, 600 manufactured by Toto Kasei Co., Ltd. Brominated bisphenol A type epoxy resin, trade name Epicoat 152, 154 manufactured by Yuka Shell Epoxy Co., Ltd., trade name EPPN-201 manufactured by Nippon Kayaku Co., Ltd., BREN, trade name DEN-438 manufactured by Dow Chemical Co., Ltd. Such as phenol novolac type epoxy resin, trade name YDCN-702, 703 manufactured by Tohto Kasei Co., Ltd., trade name EOCN manufactured by Nippon Kayaku Co., Ltd. 125S, 103S, 104S, etc. o-cresol novolac type epoxy resins, Todo Kasei Co., Ltd. trade name YD-171 etc., flexible epoxy resin, Yuka Shell Epoxy Co., Ltd. trade name Epon 1031S, Ciba Trade names Araldite 0163 manufactured by Specialty Chemicals Co., Ltd., trade names Denacol EX-611, EX-614, EX-622, EX-512, EX-521, EX-521, EX- manufactured by Nagase Chemtech Co., Ltd. 411, EX-321 polyfunctional epoxy resin, Yuka Shell Epoxy Co., Ltd. trade name Epicoat 604, Toto Kasei Co., Ltd. trade name YH-434, Mitsubishi Gas Chemical Co., Ltd. trade name TETRAD -X, TETRAD-C, Nippon Kayaku Co., Ltd. trade name GAN, Sumitomo Chemical Co., Ltd. trade name ELM-120, and other amine type epoxy resins, Heterocyclic epoxy resins such as the product name Araldite PT810 manufactured by Peachty Chemicals, Inc., the product names Celoxide 2021, EHPE3150 manufactured by Daicel Chemical Industries, Ltd., ERL4234 manufactured by UCC, etc., Dainippon Bisphenol S type epoxy resin such as Epiklon EXA-1514 manufactured by Ink Chemical Industry Co., Ltd., Triglycidyl isocyanurate such as TEPIC manufactured by Nissan Chemical Industry Co., Ltd., trade name YX manufactured by Yuka Shell Epoxy Co., Ltd. Bisphenol-type epoxy resins such as -4000 and bisphenol-type epoxy resins such as YL-6056 manufactured by Yuka Shell Epoxy Co., Ltd., and the like may be used alone or in combination of two or more. Absent.

  Among these epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin having more than two epoxy groups in one molecule, o-cresol novolac type epoxy resin, amine type epoxy resin are It is a non-halogen type, and is preferred in terms of compatibility with the urethane-modified polyimide resin of component (A), solvent resistance, chemical resistance, and moisture resistance.

  The amount of the (B) component epoxy resin used in the present invention is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, with respect to 100 parts by mass of the component (A) urethane-modified polyimide resin. Especially preferably, it is 3-30 mass parts. When the amount of the epoxy resin is less than 1 part by mass, solder heat resistance, solvent resistance, chemical resistance, and moisture resistance tend to decrease. When the amount exceeds 50 parts by mass, low warpage, mechanical properties, heat resistance, The varnish stability and the compatibility with the modified polyimide resin tend to decrease.

  Moreover, in this invention, when (B) component is added to (A) component, when the total non-volatile content of a urethane-modified polyimide-type resin composition and the paste which consists of it is 100 mass%, Preferably it is 40-90. % By mass. More preferably, it is 45-80 mass%.

  The epoxy resin of component (B) used in the present invention may further contain an epoxy compound having only one epoxy group in one molecule as a diluent.

  As an addition method of the epoxy resin, the epoxy resin to be added in advance may be dissolved after being dissolved in the same solvent as that contained in the urethane-modified polyimide resin, or directly added to the urethane-modified polyimide resin. Also good.

<Inorganic or organic fine particle (C) component>
To the urethane-modified polyimide resin composition of the present invention, an inorganic or organic filler is added as the component (C) in order to improve the workability during coating and printing and the film properties before and after film formation.

The inorganic or organic filler used in the present invention is not particularly limited as long as it can be dispersed in the above urethane-modified polyimide resin to form a paste and can impart thixotropic properties to the paste. Examples of such inorganic fillers include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), silicon nitride (Si ₃ ). N _4), barium titanate (BaO · TiO _2), barium carbonate (BaCO _3), lead titanate (PbO · TiO _2), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga ₂ O _3), spinel _{(MgO · Al 2 O 3)} , mullite _{(3Al 2 O 3 · 2SiO 2} ), cordierite _{(2MgO · 2Al 2 O 3 ·} 5SiO 2), talc (3MgO · 4SiO ₂ · H ₂ O), aluminum titanate _{(TiO 2 -Al 2 O 3)} , yttria-containing zirconia _{(Y 2 O 3 -ZrO 2)} , silicate barium (BaO · 8S O _2), boron nitride (BN), calcium carbonate (CaCO _3), calcium sulfate (CaSO _4), zinc oxide (ZnO), magnesium titanate (MgO · TiO _2), barium sulfate (BaSO _4), organic bentonite, Carbon (C) or the like can be used, and these may be used alone or in combination of two or more. Silica fine particles (trade name Aerogel manufactured by Nippon Aerosil Co., Ltd.) are preferable from the viewpoint of imparting color tone, transparency, mechanical properties and thixotropy of the obtained paste.

  The inorganic filler used in the present invention preferably has an average particle size of 50 μm or less and a maximum particle size of 100 μm or less, more preferably an average particle size of 20 μm or less, and most preferably an average particle size of 10 μm or less. The average particle diameter (median diameter) referred to here is determined on a volume basis using a laser diffraction / scattering particle size distribution measuring apparatus. When the average particle diameter exceeds 50 μm, it becomes difficult to obtain a paste having sufficient thixotropy, and the flexibility of the coating film is lowered. When the maximum particle diameter exceeds 100 μm, the appearance and adhesion of the coating film tend to be insufficient.

  The organic filler used in the present invention is not limited as long as it can be dispersed in the above urethane-modified polyimide resin solution to form a paste and can impart thixotropic properties to the paste. Polyimide resin particles, benzoguanamine resin particles, epoxy Examples thereof include resin particles.

  The amount of the inorganic or organic filler used in the present invention is preferably 1 to 25% by mass when the total nonvolatile content of the urethane-modified polyimide resin composition and the paste made thereof is 100% by mass. More preferably, it is 2-15 mass%, Most preferably, it is 3-12 mass%. If the blending amount of the inorganic or organic filler is less than 1 part by mass, the printability tends to decrease, and if it exceeds 25% by mass, the mechanical properties such as the flexibility of the coating film and the transparency tend to decrease.

<Non-halogen flame retardant (D) component>
To the modified polyimide resin composition of the present invention, a non-halogen flame retardant that dissolves in the urethane-modified polyimide resin composition is added as component (D). By adding this component, not only flame retardancy but also surprisingly improved properties such as low warpage are effective.

  The non-halogen flame retardant used in the present invention is not particularly limited as long as it is soluble in the above urethane-modified polyimide resin composition, but it has hydrolysis resistance, heat resistance and surface bleed. From these, phosphazene and phosphinic acid derivatives are preferred. You may use these individually or in combination of 2 or more types.

  As phosphazenes, for example, cyclic phenoxyphosphazenes such as trade name SPE-100 manufactured by Otsuka Chemical Co., Ltd., cyclic cyanophenoxyphosphazenes such as trade name FP-300 manufactured by Fushimi Pharmaceutical Co., Ltd., manufactured by Otsuka Chemical Co., Ltd. In addition, cyclic phenoxy phosphazenes such as SPH-100, chain phenoxy phosphazenes, cross-linked phenoxy phosphazenes, and the like are listed. However, chain phosphazenes generally have phosphorus groups compared to emotional phosphazenes because they have substituents at the molecular ends. The content is reduced. Accordingly, in the present invention, cyclic phosphazenes are preferable, and cyclic trimers and / or tetrameric phosphazenes are more preferable.

  In addition, non-reactive phosphazenes may cause bleeding on the surface over time, may elute free phosphorus under the influence of hydrolysis under severe use conditions, or the insulation properties may deteriorate due to decomposition products. Therefore, most preferably, a reactive phosphazene having a functional group that reacts with the epoxy resin is selected. Specific examples thereof include cyclic hydroxyphenoxyphosphazene having a hydroxyl group.

  Examples of phosphinic acid derivatives include HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and HCA-HQ (10- (2,5-dihydroxyphenyl)- 10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide), 10- (2,5-dihydroxynaphthyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, BCA ( 10-benzyl-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide), phenylphosphinic acid, diphenylphosphinic acid and the like.

  Among these phosphinic acid derivatives, HCA and HCA-HQ have reactivity with epoxy resins, but they may cause bleed on the surface and may be inferior in solubility in non-nitrogen solvents, so performance such as low warpage is also considered. And select as appropriate.

  In addition to the above non-halogen flame retardants, other non-halogen flame retardants may be used in combination as required as long as the low warpage, heat resistance, and bleeding are not impaired. Examples include phosphorus-containing epoxy resins copolymerized with HCA and condensed phosphate esters such as resorcyl diphenyl phosphate, but are not limited to these, and two or more types may be used in combination.

  The phosphorus content in the urethane-modified polyimide resin composition of the present invention needs to satisfy 2.0 to 5.0% by mass, and the addition amount of the component (D) is adjusted so as to be in this range. Preferably they are 2.5 mass% or more and 4.8 mass% or less. When the phosphorus content is less than 2.0% by mass, good flame retardancy cannot be obtained. On the other hand, if it exceeds 5.0% by mass, the mechanical properties, heat resistance, adhesion and insulation properties of the coating film are deteriorated.

<Curing accelerator (E) component>
To the urethane-modified polyimide resin composition of the present invention, a curing accelerator is added as a component (E) in order to further improve properties such as adhesion, chemical resistance, and heat resistance. The curing accelerator used in the present invention is not particularly limited as long as it can accelerate the curing reaction between the urethane-modified polyimide resin, epoxy resin and non-halogen flame retardant.

Specific examples of such epoxy resin curing agents, for example, Shikoku Chemicals _{Corp., 2MZ, 2E4MZ, C 11 Z} , C 17 Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C 11 Z -CN, 2PZ-CN, 2PHZ- CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C 11 Z -AZINE, 2MA-OK, 2P4MHZ, 2PHZ, imidazole derivatives such 2P4BHZ , Guanamines such as acetoguanamine and benzoguanamine, polyaminos such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine and polybasic hydrazides, organic acid salts thereof and / Or d Xiaduct, amine complex of boron trifluoride, triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine, trimethylamine, triethanol Amine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, DBU ( 1,8-diazabicyclo [5,4,0] -7-undecene), tertiary amines such as DBN (1,5-diazabicyclo [4,3,0] -5-nonene), organic acid salts thereof and / Or tetraphenylboronate, polyvinylphenol, polyvinylphenol bromide, tributyl Organic phosphines such as phosphine, triphenylphosphine, tris-2-cyanoethylphosphine, tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosphonium chloride, tetraphenylphosphonium tetraphenylboronate, etc. Quaternary ammonium salts such as quaternary phosphonium salts, benzyltrimethylammonium chloride, phenyltributylammonium chloride, the polycarboxylic acid anhydride, diphenyliodonium tetrafluoroboroate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenyl Thiopyrylium hexafluorophosphate, Irgacure 261 (Ciba Specialty Chemicals), Optoma-SP 170 (manufactured by ADEKA), photocationic polymerization catalyst, styrene-maleic anhydride resin, equimolar reaction product of phenyl isocyanate and dimethylamine, organic polyisocyanate such as tolylene diisocyanate, isophorone diisocyanate and dimethylamine, etc. Molar reactants and the like. You may use these individually or in combination of 2 or more types. Preferably, it is a curing accelerator having latent curability, and examples thereof include DBU, DBN organic acid salts and / or tetraphenylboronate, and a photocationic polymerization catalyst.

  As for the usage-amount of a hardening accelerator, 0-30 mass parts is preferable with respect to 100 mass parts of said epoxy compounds. If it exceeds 30 parts by mass, the storage stability of the urethane-modified polyimide resin composition and the heat resistance of the coating film decrease.

<Urethane-modified polyimide resin composition and paste comprising the same>
The urethane-modified polyimide resin composition of the present invention and the paste comprising the same are the component (A), component (B), component (C), component (D), component (E) and other blends as necessary. The components are not particularly limited as long as they are obtained by blending the components preferably in the above proportions and uniformly mixing with a roll mill, a mixer, or the like, and sufficient dispersion can be obtained. Multiple kneading with three rolls is preferred.

  The urethane-modified polyimide resin composition of the present invention and the paste comprising the same preferably have a B-type viscometer viscosity at 25 ° C. of 50 dPa · s to 1000 dPa · s, more preferably 100 dPa · s to 800 dPa · s. preferable. When the viscosity is less than 50 dPa · s, there is a tendency for the paste to flow out after printing and the film thickness to be reduced. When the viscosity exceeds 1000 Pa · s, during printing, the transferability of the paste to the base material is reduced, causing blurring, and voids and pinholes in the printed film tend to increase.

  The throttling property (thixotropic property) is also important, and is preferably 1.3 or more, more preferably 2.0 or more in the measurement method described later. The upper limit is preferably 7.0 or less, and more preferably 6.0 or less. If the degree of change is less than 1.3, the flow of paste after printing becomes large and the film thickness tends to be reduced. If it exceeds 7.0, the paste tends not to flow. The degree of change can be adjusted by the amount of component (C) added as a change degree imparting agent.

  The urethane-modified polyimide resin composition of the present invention and the paste comprising the same include phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and the like, if necessary. Known conventional colorants, known conventional polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, phenothiazine, etc., known conventional thickeners such as olben, benton, montmorillonite, silicone-based, fluorine-based, high Antifoaming agents such as molecular systems, leveling agents, imidazole-based, thiazole-based, triazole-based, organoaluminum compounds, organotitanium compounds, organosilane compounds, and other coupling agents / adhesion imparting agents, triphenyl Phosphate, tricresyl phosphate, trixylenyl phosphate, triethyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, cresyl bis (2,6-xylenyl) phosphate, 2-ethylhexyl phosphate, dimethyl Phosphorus-based difficulties such as methyl phosphate, resorcinol bis (diphenol A bis (dicresyl) phosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethyl phosphate, phosphoric acid amide, organic phosphine oxide, red phosphorus Flame retardant, ammonium polyphosphate, triazine, melamine cyanurate, succinoguanamine, ethylene dimelamine, triguanamine, triazinyl cyanurate, melem, melam, tris (β-cyanoethyl) ) Nitrogen flame retardants such as isocyanurate, acetoguanamine, guanylmelamine sulfate, melem sulfate, melam sulfate, metal salt systems such as potassium diphenylsulfone-3-sulfonate, aromatic sulfonimide metal salt, alkali metal polystyrene sulfonate Flame retardants, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, tin oxide and other hydrated metal flame retardants, silica, aluminum oxide, iron oxide, oxidation Titanium, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide, tungsten oxide, zinc borate, zinc metaborate, metaboro Acid barium Known flame retardants / flame retardants such as inorganic flame retardants such as rubber, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc stannate, silicone powder, thermal stabilizers, antioxidants, lubricants, etc. Conventional additives can be used.

<Curing coating>
For example, the urethane-modified polyimide resin composition of the present invention and the paste comprising the same are cured as follows as a solder resist to obtain a cured product. That is, the composition of the present invention is applied to a flexible printed wiring board with a film thickness of 5 to 80 μm by a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a curtain coating method, etc. After preliminary drying at 60 to 120 ° C., the film is finally dried at 120 to 200 ° C. Drying may be in air or in an inert atmosphere.

  The urethane-modified polyimide resin composition of the present invention thus obtained and the paste comprising the same are useful as a film forming material for semiconductor elements, overcoat inks for various electronic components, solder resist inks, and interlayer insulating films. In addition, it can be used as a paint, a coating agent, an adhesive or the like.

  In order to describe the present invention more specifically, examples will be given below, but the present invention is not limited to the examples. In addition, the measured value described in the Example is measured by the following method.

<Logarithmic viscosity>
The urethane-modified polyimide resin was dissolved in N-methyl-2-pyrrolidone so that the polymer concentration was 0.5 g / dl, and the solution viscosity was measured at 30 ° C. with an Ubbelohde type viscosity tube. The logarithmic viscosity was defined by the following formula.
(Logarithmic viscosity) = (lnηrel) / C
ln: natural logarithm,
ηrel: the viscosity ratio (−) of the solution to the pure solvent by solvent fall time measurement,
C: Solution concentration (g / dl)

<Fluctuation (thixo ratio)>
Using a Brookfield BH rotational viscometer, the measurement was performed in the following procedure. A paste made of a urethane-modified polyimide resin composition was placed in a wide-mouthed light-shielding bottle (100 ml), and the liquid temperature was adjusted to 25 ° C. ± 0.5 ° C. using a constant temperature water bath. Subsequently, after stirring 40 times over 12-15 seconds using a glass rod, a predetermined rotor was installed, allowed to stand for 5 minutes, and then the scale when rotated at 20 rpm for 3 minutes was read. The viscosity was calculated by multiplying this scale by the coefficient in the conversion table. Similarly, the following formula was calculated from the viscosity value measured at 25 ° C. and 2 rpm.
Deflection = viscosity (2 rpm) / viscosity (20 rpm)
<Pot life>
After the paste made of the urethane-modified polyimide resin composition was allowed to stand at 25 ° C. for 1 month in a sealed state, the presence or absence of resin precipitation or gelation was observed.
(Judgment) ○: No abnormality △: Precipitate ×: Varnish solidification <continuous printability>
When a paste made of a urethane-modified polyimide resin composition was continuously screen-printed for 30 minutes by the method described in Example 9, resin precipitation from the paste and an increase in viscosity were observed.

<Solder heat resistance>
The obtained laminated film was immersed in a solder bath at 260 ° C. for 30 seconds in accordance with JIS-C6481, and the presence or absence of appearance abnormality such as peeling or swelling was observed.
(Judgment) ○: No appearance abnormality △: Slight appearance abnormality ×: Overall appearance abnormality

<Flexibility>
The obtained laminated film was evaluated according to JIS-K5400. The diameter of the mandrel was 2 mm, and the presence or absence of cracks was confirmed.

<Sleigh>
The obtained laminated film was cut out to 10 cm × 10 cm. A sample conditioned at 25 ° C. and 65% for 24 hours was placed on a horizontal glass plate in a convex state, and the average height of the four corners was evaluated.
(Judgment) ○: Less than 2 mm in height Δ: Less than 10 mm in height ×: More than 10 mm in height

<Adhesion>
According to JIS-K5600, 100 1-mm grids were made on the obtained laminated film, and a peel test using a cello tape was performed to observe the peeled-off state of the grids.
The same process was performed when a polyimide film having a thickness of 25 μm was used as a base material.
(Decision) ○: No peeling at 100/100 Δ: 70 to 99/100
X: 0-70 / 100

<Pencil hardness>
The obtained laminated film was evaluated according to JIS-K5400. The pencil hardness is preferably 2H or higher, and more preferably 3H or higher.

<Flame retardance evaluation>
Using the polyimide film having a thickness of 25 μm as a base material, the obtained laminated film having a thickness of 15 μm was evaluated for flame retardancy according to the UL94 standard. The flame retardancy is preferably VTM-2 or higher, and most preferably VTM-0, according to UL standards.

<Insulation characteristics>
A comb-shaped pattern with a line spacing of 50 μm was formed on a two-layer CCL (trade name Viroflex) manufactured by Toyobo, washed with 1% sulfuric acid, and then washed with water and dried. The entire surface of the paste was printed on the circuit, and the obtained solder resist layer was heated and cured at 160 ° C. for 120 minutes. The insulation resistance between lines when a DC voltage of 100 V was applied was measured.
<Chemical resistance>
The obtained laminated film was immersed in 10% HCl, 10% NaOH, isopropanol, and methyl ethyl ketone for 10 seconds each, and the presence or absence of appearance abnormality such as peeling or dissolution was observed.
(Judgment) ○: No appearance abnormality △: Slight appearance abnormality ×: Overall appearance abnormality

Production Example 1
Trimellitic anhydride (purity 99.9%, trimellitic acid content 0.1%); 166.0 mass in a four-necked 2 liter separable flask equipped with a stirrer, a condenser, a nitrogen inlet tube and a thermometer Parts, bisphenol A propylene oxide adduct (trade name Newpol BP-5P, molecular weight 530, manufactured by Sanyo Chemical Industries, Ltd.); 86.3 parts by mass, polypropylene glycol (trade name Sannix, manufactured by Sanyo Chemical Industries, Ltd.) PP2000, molecular weight 2000); 108 parts by weight, 1,6-hexamethylene isocyanate; 84.1 parts by weight, 4,4-diphenylmethane diisocyanate; 125.1 parts by weight, γ-butyrolactone; 493.5 parts by weight, and catalyst 1,8-diazabicyclo [5.4.0] -7-undecene; 1.5 parts by mass were charged under nitrogen flow, 10 ℃ temperature was raised to, and reacted for 2 hours. Next, after raising the temperature to 170 ° C. and reacting for 5 hours, 246.8 parts by mass of diglyme was added to dilute, and cooled to room temperature to obtain a dark brown urethane-modified polyimide resin solution A-1 having a nonvolatile content of 40% by mass. Obtained.

Production Example 2
Trimellitic anhydride (purity 99.9%, trimellitic acid content 0.1%); 145.3 mass in a 4-neck 2 liter separable flask equipped with a stirrer, a condenser, a nitrogen inlet tube and a thermometer; Parts, bisphenol A propylene oxide adduct (trade name Newpol BP-5P, molecular weight 530, manufactured by Sanyo Chemical Industries, Ltd.); 115.1 parts by weight, polypropylene glycol (trade name Sannix, manufactured by Sanyo Chemical Industries, Ltd.) PP1000, molecular weight 1000); 108 parts by weight, 1,6-hexamethylene isocyanate; 84.1 parts by weight, 4,4-diphenylmethane diisocyanate; 125.1 parts by weight, γ-butyrolactone; 511.1 parts by weight, and catalyst 1,4-diazabicyclo [2.2.2] octane; charged in 2.2 parts by mass and heated to 100 ° C. under a nitrogen stream. The temperature was raised and reacted for 2 hours. Next, Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.); 1.0 part by mass was added, the temperature was raised to 170 ° C. and the reaction was allowed to proceed for 5 hours. To obtain a dark brown urethane-modified polyimide resin solution A-2 having a nonvolatile content of 40% by mass.

Production Example 3
Trimellitic anhydride (purity 99.9%, trimellitic acid content 0.1%); 145.3 mass in a 4-neck 2 liter separable flask equipped with a stirrer, a condenser, a nitrogen inlet tube and a thermometer; Parts, bisphenol A ethylene oxide adduct (trade name Newpol BPE-100, molecular weight 670, manufactured by Sanyo Chemical Industries, Ltd.); 144.7 parts by mass, polypropylene glycol (trade name, SANNICS, manufactured by Sanyo Chemical Industries, Ltd.) PP1000, molecular weight 1000); 108 parts by mass, 1,6-hexamethylene isocyanate; 84.1 parts by mass, 4,4-diphenylmethane diisocyanate; 125.1 parts by mass, γ-butyrolactone; 540.7 parts by mass, and catalyst 1,4-diazabicyclo [2.2.2] octane; charged with 2.2 parts by mass, 100 ° C. under a nitrogen stream In temperature was raised and reacted for 2 hours. Next, the temperature was raised to 170 ° C. and reacted for 5 hours. Then, 270.3 parts by mass of diglyme was added and diluted, and cooled to room temperature to obtain a dark brown urethane-modified polyimide resin solution A-3 having a nonvolatile content of 40% by mass. Obtained.

Production Example 4
Trimellitic anhydride (purity 99.9%, trimellitic acid content 0.1%); 166.0 mass in a four-necked 2 liter separable flask equipped with a stirrer, a condenser, a nitrogen inlet tube and a thermometer Parts, bisphenol A propylene oxide adduct (trade name Newpol BP-5P manufactured by Sanyo Chemical Industries, Ltd., molecular weight 530); 115.1 parts by mass, 1,6-hexamethylene isocyanate; 84.1 parts by mass, 4 , 4-diphenylmethane diisocyanate; 125.1 parts by mass, γ-butyrolactone; 439.5 parts by mass, and 1,4-diazabicyclo [2.2.2] octane as a catalyst; The temperature was raised to 100 ° C. and reacted for 2 hours. Next, after raising the temperature to 170 ° C. and reacting for 5 hours, 207.2 parts by mass of diglyme was added to dilute and cooled to room temperature to obtain a dark brown urethane-modified polyimide resin solution A-4 having a nonvolatile content of 40% by mass. Obtained.

Production Example 5
Trimellitic anhydride (purity 99.9%, trimellitic acid content 0.1%) in a four-necked 2 liter separable flask equipped with a stirrer, a condenser, a nitrogen inlet tube and a thermometer; 124.5 mass Parts, bisphenol A propylene oxide adduct (trade name Newpol BP-5P, molecular weight 530, manufactured by Sanyo Chemical Industries, Ltd.); 115.1 parts by weight, polypropylene glycol (trade name Sannix, manufactured by Sanyo Chemical Industries, Ltd.) PP2000, molecular weight 2000); 432.0 parts by weight, 1,6-hexamethylene isocyanate; 84.1 parts by weight, 4,4-diphenylmethane diisocyanate; 125.1 parts by weight, γ-butyrolactone; 823.8 parts by weight, and 1,4-diazabicyclo [2.2.2] octane as a catalyst; Until the temperature was raised and reacted for 2 hours. Subsequently, after heating up to 170 degreeC and making it react for 5 hours, 411.9 mass parts of diglyme is added and diluted, The dark brown urethane-modified polyimide resin solution A-5 of 40 mass% of non volatile matters is cooled by cooling to room temperature. Obtained.

Production Example 6
Trimellitic anhydride (purity 99.9%, trimellitic acid content 0.1%) in a four-necked 2 liter separable flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube and a thermometer; 155.6 mass Parts, bisphenol A propylene oxide adduct (trade name Newpol BP-5P, molecular weight 530, manufactured by Sanyo Chemical Industries, Ltd.); 115.1 parts by weight, polypropylene glycol (trade name Sannix, manufactured by Sanyo Chemical Industries, Ltd.) PP2000, molecular weight 2000); 108.0 parts by weight, 1,6-hexamethylene isocyanate; 168.2 parts by weight, γ-butyrolactone; 475.6 parts by weight, and 1,4-diazabicyclo [2.2.2 as a catalyst. ] Octane: 2.2 parts by mass were charged, heated to 100 ° C. under a nitrogen stream, and allowed to react for 2 hours. Subsequently, after heating up to 170 degreeC and making it react for 5 hours, 237.8 mass parts of diglyme was added and diluted, and the dark brown urethane-modified polyimide resin solution A-6 with a non volatile matter of 40 mass% was cooled to room temperature. Obtained.

Production Example 7
Trimellitic anhydride (purity 99.9%, trimellitic acid content 0.1%) in a four-necked 2 liter separable flask equipped with a stirrer, a condenser, a nitrogen inlet tube and a thermometer; 199.8 mass Part, 4,4-diphenylmethane diisocyanate; 250.3 parts by mass, NMP; 831.4 parts by mass and potassium fluoride as a catalyst; 1.2 g (2 mol%) were charged, and the temperature was raised to 120 ° C. under a nitrogen stream, The reaction was performed for 2 hours. Subsequently, after heating up to 160 degreeC and making it react for 4 hours, 129.3 mass parts of NMP was added and diluted, and the dark brown polyimide resin solution A-7 with a non volatile matter of 35 mass% was obtained by cooling to room temperature. .

Example 1
Based on 48.8 parts by mass of the resin content of the urethane-modified polyimide resin solution A-1 obtained in Production Example 1, jER152 (trade name of phenol novolac epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.) 7.2 mass Part was added and diluted with diglyme. Furthermore, 3.2 parts by mass of Aerogel # 300 (Nippon Aerosil Co., Ltd. hydrophilic silica fine particles) as a filler, 19.2 parts by mass of SPE-100 (Otsuka Chemical Co., Ltd.) as a non-halogen flame retardant, BCA 19.1 parts by mass (manufactured by Sanko Co., Ltd.), 0.5 parts by mass of Ucat5002 (manufactured by Sun Apro Co., Ltd.) as a curing accelerator, and Floren AC-326F (manufactured by Kyoeisha Chemical Co., Ltd.) as an antifoaming agent. 1.5 parts by mass, adding BYK-358 (produced by Big Chemie Co., Ltd.) as a leveling agent, first kneading roughly, and then repeating kneading three times using a high-speed three-roll to uniformly disperse the filler A paste made of the urethane-modified polyimide resin composition of the present invention having thixotropic properties was obtained. When the viscosity was adjusted with diglyme, the solution viscosity was 190 poise and the throttling was 2.7. The paste made of the obtained modified polyimide resin composition was applied to the glossy surface of an electrolytic copper foil having a thickness of 18 μm so as to have a thickness of 15 μm after drying. After drying with hot air at 80 ° C. for 10 minutes, a laminated film was obtained by heating at 150 ° C. for 120 minutes in an air atmosphere. Moreover, the film was obtained by carrying out the etching removal of the copper foil of the obtained laminated | multilayer film with a ferric chloride solution. Similarly, a laminated film applied to a 25 μm-thick polyimide film (Kaneka Apical NPI) and dried and heated was obtained. The evaluation results are shown in Table 1.

Examples 2-8
A paste was prepared in the same manner as in Example 1, except that the urethane-modified polyimide resin solution was as shown in Table 1 and the components (B) to (E) were also the same as those shown in Table 1. The evaluation results are shown in Table 1.

Comparative Example 1
A paste was prepared in the same manner as in the Examples using urethane-modified polyimide resin solution A-4 and components (B) to (E) described in Table 1. The evaluation results are shown in Table 1. In this case, since polyoxyalkylene glycol was not copolymerized, the results were inferior in low warpage, continuous printability, and pot life.

Comparative Example 2
A paste was prepared in the same manner as in the Examples using urethane-modified polyimide resin solution A-7 and using components (B) to (E) listed in Table 1. The evaluation results are shown in Table 1. Since the resin does not contain a soluble component in the non-nitrogen solvent, it is necessary to add a nitrogen polar solvent. Ink whitening occurs during printing, and if it is not dried at high temperature, the soldering heat resistance is reduced due to the residual solvent. Further, warpage due to a high elastic modulus occurs and the flexibility is poor.

Comparative Example 3
A paste without epoxy resin was prepared. The evaluation results are shown in Table 1. In this case, sufficient solder heat resistance cannot be obtained and the coating film is softened.

Example 9
Urethane modification obtained in Example 1 on a copper circuit (L / S = 50/50) obtained by a subtractive method from Toyobo 2-layer CCL (trade name Viroflex, copper foil 18 μm, base material 20 μm) A paste made of a polyimide resin composition was printed on a SUS mesh plate (Murakami Co., Ltd. 150 mesh, emulsion thickness 30 μm) at a printing speed of 5 cm / sec and dried at 80 ° C. for 6 minutes in an air atmosphere. Then, the flexible printed wiring board which gave the coverlay (coating) which consists of a urethane-modified polyimide resin composition was obtained by heat-curing for 60 minutes at 150 degreeC. The thickness of the coating was 15 μm.

  The modified polyimide resin composition of the present invention thus obtained and the paste comprising the same are useful as a film forming material for overcoat inks for various electronic parts such as flexible printed wiring boards, solder resist inks, and interlayer insulating films. In addition, since it can be used in a wide range of electronic devices as paints, coating agents, adhesives, etc., it is a major industrial investment.

Claims (7)

As component (A), (a) a trivalent and / or tetravalent polycarboxylic acid derivative having an acid anhydride group, (b) a polyoxyalkylene glycol (c) a polyalkylene of bisphenol represented by the general formula (1) Oxide adduct (d) Urethane-modified polyimide resin (B) component having an aliphatic polyamine residue derivative as an essential component, an epoxy resin having two or more epoxy groups per molecule,
(C) A urethane-modified polyimide resin composition containing an inorganic or organic filler as a component.

(In the formula (1), m and n are integers of 1 or more and may be the same or different, R1 is an alkylene group having 1 to 20 carbon atoms, R2 and R3 are hydrogen or 1 carbon atom. To 4 alkyl groups, which may be the same or different) The urethane-modified polyimide resin composition according to claim 1, further comprising a non-halogen flame retardant that dissolves in the urethane-modified polyimide resin as component (D). The urethane-modified polyimide resin composition according to claim 1 or 2, further comprising a curing accelerator as component (E). The urethane-modified polyimide resin is a urethane-modified polyimide resin obtained by reacting in an organic solvent selected from ether solvents, ester solvents, ketone solvents, and aromatic hydrocarbon solvents, and does not perform solvent substitution. The urethane-modified polyimide resin composition according to any one of claims 1 to 3, which contains no solvent other than the above. The urethane-modified polyimide resin composition according to any one of claims 2 to 4, wherein the non-halogen flame retardant is a phosphazene and / or a phosphinic acid derivative. The paste which consists of a urethane-modified polyimide resin composition as described in any one of Claim 1 to 5 which has thixotropic property of 1.3 or more by a throttling degree. An electronic component having a solder resist layer, a surface protective layer, an interlayer insulating layer or an adhesive layer obtained by drying and curing the urethane-modified polyimide resin composition according to any one of claims 1 to 6 or a paste made thereof.