KR20110063428A - Polyamide resin, resin composition thereof, flame-retardant adhesive composition and adhesive sheet made of said composition, coverlay film, and printed wiring board - Google Patents

Abstract

The present invention simultaneously satisfies heat resistance, adhesiveness, insulation reliability, and solvent solubility, and provides a polyamideimide resin suitable for heat resistant adhesives for printed wiring board applications. In addition, the present invention is a non-halogen, flame-retardant adhesive that contains components that are all soluble in general purpose solvents and exhibits stable characteristics, and can also be used for flexible printed wiring boards and the like, and exhibit excellent flame resistance, solder heat resistance, adhesiveness, and electrical insulation. To provide a composition.
The present invention is a polyamideimide resin obtained by reacting an acid component of the following (a) to (c) with a diisocyanate or diamine having an aromatic ring, wherein the total acid component of the polyamideimide resin is 100 mol%. The ratio of each acid component is (a) 3 mol%-10 mol%, (b) 10 mol%-80 mol%, (c) 10 mol%-87 mol%, It is related with the polyamideimide resin characterized by the above-mentioned. :
(a) acrylonitrile-butadiene rubber having carboxyl groups at both ends,
(b) aliphatic dicarboxylic acids having 4 to 12 carbon atoms,
(c) Acid anhydride of polycarboxylic acid which has an aromatic ring.

Description

POLYAMIDE RESIN, RESIN COMPOSITION THEREOF, FLAME-RETARDANT ADHESIVE COMPOSITION AND ADHESIVE SHEET MADE OF SAID COMPOSITION, COVERLAY FILM , AND PRINTED WIRING BOARD}

The present invention relates to a polyamideimide resin and a thermosetting resin composition using the resin. More specifically, the present invention relates to a copper clad laminate, a coverlay, an adhesive sheet, and a resin, having excellent flexibility, heat resistance, solvent solubility, insulation, and adhesiveness. The present invention relates to an adhesive resin composition suitable for printed wiring boards such as attached copper foil, overcoat ink, and prepreg.

The present invention also provides a flame-retardant adhesive composition which exhibits excellent performance in printed wiring boards, particularly flexible printed wiring boards requiring flexibility, and has excellent flame retardancy, solder heat resistance, adhesion, and electrical insulation, and a copper clad laminate using the composition, It is related with printed wiring boards, such as an adhesive sheet, a coverlay film, copper foil with resin, a prepreg, and overcoat ink.

Conventionally, polyamideimide resins contain aromatic monomers and exhibit properties such as heat resistance, chemical resistance, and abrasion resistance comparable to polyimide, and are superior to polyimide as N-methyl-2-pyrrolidone and the like. Because of its high boiling point and its solubility in a special amide solvent, it is applied to molding materials, heat-resistant insulating paints and the like. However, aromatic polyamideimide resins, like general polyimide resins, generally have high elastic modulus, are hard and brittle, and have low solubility in low boiling point solvents, and thus require flexibility such as adhesives and ease of drying of solvents. Use to use was hard.

By the way, a flexible printed wiring board is a board | substrate for display device devices, such as a liquid crystal display and a plasma display, such as a liquid crystal display and a plasma display, which require flexibility and space saving, board relay cables, such as a mobile telephone, a digital camera, a portable game machine, and an operation switch part. It is widely used in board | substrates etc., and expansion of a use is anticipated further.

As adhesives used for such applications, epoxy resins and acrylic resins have conventionally been used. However, in order to cope with recent densification of wiring and lead-free solder orientation, heat resistance is insufficient, and as an adhesive having heat resistance to replace them, polyimide System resins have been examined. Copolymerization of long-chain monomers and oligomers with polyimide resins for solving the drawbacks of the high elastic modulus of conventional polyimide resins, that they are hard and brittle, difficult to develop adhesiveness, and that they are soluble in solvents of high boiling point. Review is made. For example, Patent Documents 1 and 2 disclose polysiloxane-modified polyimide resins as a method of providing flexibility and low elastic modulus.

However, polysiloxane-modified polyimide-based resins need to use starting materials having very expensive dimethylsiloxane bonds in order to impart flexibility and lower elastic modulus, resulting in poor economic efficiency. Moreover, there exists a problem that the adhesiveness and solubility of resin fall with the increase of the copolymerization amount of polysiloxane.

As a solution to this problem, Patent Literature 3 and Patent Literature 4 disclose compositions using polycarbonate-modified polyimide-based resins, and drawbacks such as low solubility and economy are improved. However, in order to achieve sufficient flexibility and low elastic modulus, It is necessary to increase the amount of carbonate modification, in which case the chemical resistance and the moist heat resistance tend to be lowered.

In addition, Patent Document 5 discloses a method of copolymerizing polyols such as polyethylene glycol, polypropylene glycol polytetramethylene glycol, and the like with a polyamideimide resin. However, these modified polyamideimide has a problem that the heat resistance is lowered because the long-chain polyol is copolymerized with a urethane bond having poor heat resistance.

In addition, Patent Document 6 discloses a method of copolymerizing dimer acid to polyamideimide. Also in this method, although flexibility can be given to some extent, since molecular weight of a dimer acid is comparatively low, in order to express sufficient flexibility, it is necessary to increase a copolymerization amount, and in that case, the ratio of the aromatic group in resin is remarkable. Since it falls, heat resistance falls. In addition, by increasing the amount introduced into the resin, there is a problem that the glass transition temperature is lowered and that the adhesion and the solubility are lowered.

Patent Documents 7 and 8 disclose methods for copolymerizing acrylonitrile butadiene having a carboxyl group at both ends of a molecule in a polyamideimide resin. This method also provides flexibility and some degree of adhesiveness improvement, but in order to express sufficient adhesiveness by this method, it is necessary to increase the copolymerization amount of acrylonitrile butadiene, and as a result, insulation reliability is high. Moreover, solvent solubility falls and it becomes difficult to melt | dissolve other than high boiling point solvents, such as N-methyl- 2-pyrrolidone. To be suitably used as an adhesive, it is necessary to dissolve in a low boiling point solvent such as dimethyl acetylamide and toluene, and in the use of printed wiring boards, the appearance of a resin excellent in all of heat resistance, flexibility, insulation reliability, adhesion, and solvent solubility is desired. It is becoming.

Currently, flexible printed wiring boards are used for device-mounting boards for display devices such as electronic device components such as liquid crystal displays and plasma displays that require flexibility and space saving, and substrates such as mobile phones, digital cameras, portable game machines, and personal computers. It is widely used for relay cables, operation switch boards and the like. In recent years, these electronic device components have become smaller and higher in density, and the demand for fine patterning and high performance of flexible printed wiring boards is increasing, and in particular, further improvements such as flame retardancy, solder heat resistance, adhesion, and electrical insulation are It is needed.

The flame retardancy of these electronic device parts is for the purpose of ensuring safety against fire, and bromine flame retardants have been used as a flame retardant imparting agent. However, while the environmental impact is important as a social problem, bromine-based halogen compounds may generate corrosive hydrogen halide gas with time, but when burned, the same gas, dioxins, furans, etc. There is a fear of generating a substance that adversely affects. For this reason, the movement which suppresses use of a halogen compound becomes high, and the halogen free flame-retardant adhesive agent is calculated | required.

In view of the above background, recently, as a flame retardant to replace a halogen compound, a method of flame retarding using a filler such as a phosphorus compound, a metal hydrate, a nitrogen-containing compound, or the like has been proposed. However, non-halogen-based flame retardants do not contain harmful halogens, but are inferior to the flame-retardant effect compared to halogen-based flame retardants, and thus tend to require a large amount of flame retardants. The addition of a large amount of flame retardant causes bleeding out of the flame retardant, deterioration of mechanical properties of the adhesive, and the like, and therefore it is difficult to achieve both flame retardancy and various characteristics.

In addition, the filler such as the metal hydrate described above requires a step for uniformly dispersing the filler in the adhesive composition, and the process is increased compared to the case where no filler is included, resulting in inferior economic efficiency. In addition, due to the settling of the filler, non-uniformity of the adhesive composition component is likely to occur, and the varnish usage period of the composition is short, so that quality control is difficult. There are a variety of problems, such as dilution of chemicals, reducing performance.

Also in the phosphorus compound, phosphate esters often used as flame retardants are often susceptible to hydrolysis, and when phosphate ester is used as a flame retardant, attention should be paid to the addition amount and structure thereof. For example, although the resin compositions containing phosphate ester are proposed in patent documents 9-11 etc., a phosphate ion component is generated under high temperature, high humidity conditions, electrical insulation fall, adhesiveness, and solvent resistance fall, and a satisfactory characteristic is obtained. I do not lose.

With respect to such a problem, a flame-retardant resin composition (Patent Document 12) containing an epoxy resin, a curing agent, and a phosphine oxide has been proposed, and chemical resistance is improved by using phosphine oxide. However, in evaluation of the flame retardance of the laminated board which consists of the said composition, all the outermost surfaces contain copper foil, the contact surface of oxygen and a composition is small, and it is set as the structure by which flame-retardant UL-94V0 is obtained easily. In addition, the solder heat resistance is also low at 260 ° C., and high performance of flexible printed wiring boards is required. Today, the composition disclosed herein cannot be said to have sufficient heat resistance and flame resistance.

Moreover, the resin composition (patent document 13) containing a phosphorus containing epoxy resin and a hardening | curing agent is proposed, and by reacting the reactive phosphorus compound with an epoxy resin, by the bleed out from the laminated body which was a problem with the additive phosphorus compound. Problems such as a drop in electrical characteristics can be solved. However, since the phosphorus content rate of the phosphorus containing epoxy resin used practically for a flexible printed wiring board is low around 3 mass%, sufficient flame retardance is not obtained. Also in the said composition (patent document 13), since flame retardance is evaluated by the structure obtained easily flame retardance as mentioned above, it cannot be said that it has sufficient flame retardance. Moreover, when phosphorus content rate is raised in order to improve flame retardance, an epoxy group equivalent will reduce, sufficient crosslinked structure will not be obtained, a problem of inferior heat resistance, and the problem that the solubility to a solvent worsens will arise.

In addition to the above, there have been many proposals for flame retardants using reactive phosphorus compounds and phosphorus-containing epoxy resins, for example, adhesive compositions containing phosphorus-based flame retardants, thermoplastic resins and thermosetting resins (Patent Document 14), nitrogen-containing compounds, epoxy resins, phosphorus Coverlays (patent document 15) and the like containing an adhesive composition containing an atom-containing non-epoxy compound and a curing agent have been proposed. However, in any of the examples, it is possible to assume that all of the inorganic fillers are added and that various properties such as flame retardancy and heat resistance cannot be satisfied without the filler. The addition of the filler has the same problems as described above, and in Patent Document 14, the solder heat resistance is insufficient despite the addition of the filler, and also in Patent Document 15, since the addition type phosphate ester is added, hydrolysis resistance Falls behind

As mentioned above, in halogen-free flame-retardant adhesive agent, it is a phenomenon that it is difficult to make both flame retardance and various characteristics compatible.

Patent Document 1: Japanese Patent Application Laid-Open No. 5-25452 Patent Document 2: Japanese Patent Application Laid-Open No. 7-304950 Patent Document 3: Japanese Patent Application Laid-Open No. 11-12500 Patent Document 4: Japanese Patent No. 3928329 Patent Document 5: Japanese Patent No. 3729291 Patent Document 6: Japanese Patent Application Laid-Open No. 3-54690 Patent Document 7: Japanese Patent Application Laid-Open No. 2003-289594 Patent Document 8: Japanese Patent No. 3931387 Patent Document 9: Japanese Patent Application Laid-Open No. 2000-345035 Patent Document 10: Japanese Patent Application Laid-Open No. 2001-339131 Patent Document 11: Japanese Unexamined Patent Publication No. 2001-339132 Patent Document 12: Japanese Patent Application Laid-Open No. 2001-200140 Patent Document 13: Japanese Patent Laid-Open No. 2001-288247 Patent Document 14: Japanese Patent Application Laid-Open No. 2002-146310 Patent Document 15: Japanese Patent Application Laid-Open No. 2004-87923

As mentioned above, in the prior art, the polyimide resin suitable as a heat resistant adhesive agent which can be used for the use of printed wiring boards which satisfy | fills heat resistance, flexibility, adhesiveness, insulation reliability, and solvent solubility simultaneously is not obtained. This invention solves the problem of said prior art, and makes it a subject to provide the polyamide-imide resin suitable for the use of printed wiring boards, etc., and the adhesive resin composition using this resin.

Furthermore, it is non-halogen, contains no fillers, contains all soluble components in general-purpose solvents, and exhibits stable characteristics, and also shows excellent flame resistance, solder heat resistance, adhesiveness, and electrical insulation property in flexible printed wiring boards and the like. It is providing the flame-retardant adhesive composition which can be used, and also providing the printed wiring boards, such as a copper clad laminated board, an adhesive sheet, a coverlay film, a prepreg, the copper foil with resin, and an overcoat ink using the said composition.

MEANS TO SOLVE THE PROBLEM The present inventors came to complete this invention finally as a result of earnestly research in order to solve the said subject. That is, this invention includes the following structures.

(One)

A polyamideimide resin obtained by reacting a diisocyanate or diamine having an aromatic ring with an acid component of the following (a) to (c), each acid component when the total acid component of the polyamideimide resin is 100 mol%. Wherein the ratio of (a) 3 mol% to 10 mol%, (b) 10 mol% to 80 mol%, and (c) 10 mol% to 87 mol%:

(a) acrylonitrile-butadiene rubber having carboxyl groups at both ends,

(b) aliphatic dicarboxylic acids having 4 to 12 carbon atoms,

(c) Acid anhydride of polycarboxylic acid which has an aromatic ring.

(2)

The polyamideimide resin is dissolved in a mixed solvent containing 60 mass of at least one solvent selected from the group consisting of ethanol, toluene, xylene and methyl ethyl ketone and 40 mass of dimethylacetamide, at least 10 mass% at 25 ° C. Polyamideimide resin according to the above.

(3)

The polyamideimide resin composition which added the thermosetting component to the polyamideimide resin as described in said (2).

(4)

The polyamideimide resin composition as described in said (3) whose thermosetting component is an epoxy resin.

(5)

The printed wiring board using the polyamide-imide resin composition as described in said (3) or (4) as an adhesive agent.

(6)

(A) polyamideimide resin, (B) phosphorus containing epoxy resin, (C) phosphorus compound, and (A) polyamideimide resin which has the acid component and aromatic ring of following (a)-(c) It is a polyamideimide resin obtained by making isocyanate or diamine react, and when the total acid component of the said polyamideimide resin is 100 mol%, the ratio of each acid component is (a) 3 mol%-10 mol%, (b) It is 10 mol%-80 mol%, (c) 10 mol%-87 mol%, The flame-retardant adhesive characterized by the phosphorus content rate with respect to the total mass of (A)-(C) component 2.0 mass%-5.0 mass%. Composition:

(a) acrylonitrile-butadiene rubber having carboxyl groups at both ends,

(b) aliphatic dicarboxylic acids having 4 to 12 carbon atoms,

(c) Anhydrides of polycarboxylic acids having an aromatic ring.

(7)

(C) The flame-retardant adhesive composition according to 6 above, wherein the phosphorus compound is a phosphazene and / or phosphinic acid derivative.

(8)

(D) The flame-retardant adhesive composition according to the above 6 or 7, which further contains an epoxy resin curing agent.

(9)

(E) The flame-retardant adhesive composition in any one of said 6-8 containing the epoxy resin which does not contain phosphorus.

10

(F) The flame-retardant adhesive composition in any one of said 6-9 which further contains a silane coupling agent.

(11)

All of the said (A)-(F) component in any one of said 6-10 which melt | dissolve in 25 mass% of solid content concentration 25 degreeC in the solvent in any one of dimethyl acetamide, ethanol, toluene, xylene, and methyl ethyl ketone. Flame retardant adhesive composition.

(12)

The flame-retardant adhesive composition in any one of said 6-11 whose phosphorus content rate with respect to the total mass of the said (A)-(F) component is 2.0 mass%-5.0 mass%.

(13)

The adhesive sheet which has a layer in which the flame-retardant adhesive composition in any one of said 6-12 is made into an adhesive bond layer, and the adhesive bond layer containing the flame-retardant adhesive composition in any one is laminated | stacked on the peelable protective film.

(14)

The coverlay film in which the adhesive bond layer and insulating plastic film containing the flame-retardant adhesive composition in any one of said 6-12 are laminated | stacked.

(15)

The flexible printed wiring board containing the insulating layer formed using the flame-retardant adhesive composition in any one of said 6-12.

Since the polyamideimide resin of this invention copolymerizes the acrylonitrile butadiene rubber which has a carboxyl group in both terminals as an acid component and the aliphatic dicarboxylic acid of 4-12 carbons in a specific range, it melt | dissolves also in a low boiling point solvent. Not only is it possible, the adhesiveness of the polyamideimide resin itself is remarkably improved. For this reason, the heat resistance, flexibility, adhesiveness, insulation reliability, and solvent solubility which were difficult to satisfy simultaneously at the same time can be satisfied simultaneously, and a heat resistant adhesive suitable for a printed wiring board can be provided.

In addition, since the flame-retardant adhesive composition of the present invention is non-halogen, does not contain an inorganic filler such as aluminum hydroxide, and can achieve the flame retardancy of UL94 VTM-0, and also includes all soluble components in a general purpose solvent, There is no worry about the problem of dispersing, it is excellent in stability, and it is easy to manufacture a thin film with stable characteristics. Moreover, since it is a composition melt | dissolved in the general purpose solvent of the low boiling point, drying is easy and it is suitable as a flame-retardant adhesive agent.

Moreover, when the flame-retardant adhesive composition of this invention is used as an adhesive agent of a printed wiring board, it shows the outstanding flame retardance, solder heat resistance, adhesiveness, and electrical insulation. Moreover, even if it is left under high temperature, high humidity, and moisture-absorbed, the outstanding solder heat resistance which has not existed conventionally can be exhibited. Moreover, even after the PCT test of high temperature, high humidity conditions, high adhesiveness can be maintained. In addition, the coverlay provided on the circuit can exhibit a high degree of migration resistance.

Hereinafter, the present invention will be described in detail.

1. Polyamideimide Resin

The polyamideimide resin of the present invention is a polyamideimide resin obtained by reacting an acid component of the following (a) to (c) with a diisocyanate or diamine having an aromatic ring, and 100 mol of all the acid components of the polyamideimide resin. In the case of%, the ratio of each acid component is (a) 3 mol%-10 mol%, (b) 10 mol%-80 mol%, (c) 10 mol%-87 mol%:

(a) acrylonitrile-butadiene rubber having carboxyl groups at both ends,

(b) aliphatic dicarboxylic acids having 4 to 12 carbon atoms,

(c) Acid anhydride of polycarboxylic acid which has an aromatic ring.

The acrylonitrile-butadiene rubber having a carboxyl group at both ends of the present invention is copolymerized in an amount of 3 mol% to 10 mol% of all acid components in order to provide flexibility and adhesion to the polyamideimide resin. Preferably it is 3 mol%-8 mol%, and when copolymerization amount is less than 3 mol%, flexibility and adhesiveness cannot express, and when it exceeds 10 mol%, there exists a tendency for insulation reliability and solubility to a low boiling point solvent to fall. .

As acrylonitrile-butadiene rubber which has a (a) carboxyl group in both terminal in this invention, it is preferable that it has an acrylonitrile site | part and a butadiene site | part, and a weight average molecular weight is 500-5000. If molecular weight is smaller than this range, flexibility and adhesiveness cannot be expressed, and if molecular weight is large, it will become difficult to copolymerize in a polyamideimide resin. Moreover, it is preferable that the ratio of an acrylonitrile site | part is the range of 10 mass%-50 mass%. If it is less than 10 mass%, there exists a tendency for the solubility to a low boiling point solvent to fall, and when it exceeds 50 mass%, there exists a tendency for insulation reliability to fall.

As acrylonitrile butadiene rubber which has a commercially available carboxyl group which satisfy | fills these at both ends, the emerald performance material company Hypro (trade name) CTBN series etc. are mentioned, for example. However, only copolymerizing the component (a) does not have sufficient flexibility, adhesiveness and solubility.

The aliphatic dicarboxylic acid having 4 to 12 carbon atoms (b) in the present invention is copolymerized with polyamideimide resin in order to improve flexibility, adhesiveness and solvent solubility. Copolymerization amount is 10 mol%-80 mol% copolymerization of all the acid components, Preferably it is 20 mol%-60 mol%. When it is less than 10 mol%, sufficient adhesiveness and flexibility are not obtained and the effect of solubility improvement is also small. When it exceeds 80 mol%, heat resistance falls because the ratio of the aromatic structure in polyamideimide resin falls.

As described above, the amount of the acrylonitrile-butadiene rubber having (a) component carboxyl groups at both ends is limited, and the component (a) alone may exhibit sufficient adhesiveness, flexibility, and solubility in a low boiling point solvent. Can't. Therefore, it is necessary to copolymerize (b) component.

Here, carbon number of the dicarboxylic acid of (b) component is also the number containing carbon of a carboxylic acid part, Therefore, in the case of sebacic acid, for example, it is set to 10. Moreover, when this carbon number is larger than 12, there exists a problem that many parts with low polarity in polyamideimide resin fall, and the solubility and adhesiveness of resin fall.

Examples of the aliphatic dicarboxylic acid having 4 to 12 carbon atoms (b) in the present invention include linear aliphatic dicarboxylic acids and aliphatic dicarboxylic acids having a branched structure. For example, succinic acid, glutaric acid, adipic acid, heptane diacid, octanoic acid, azelaic acid, sebacic acid, undecane diacid, dodecane diacid, etc. are mentioned as a thing of a linear structure, As what has a branched structure, The thing which has a substituent of a hydrocarbon in the said dicarboxylic acid, such as 2-methylsuccinic acid, is mentioned, These may be used independently and may be used in combination of plurality.

Examples of the acid anhydride of the polycarboxylic acid having an (c) aromatic ring which plays a role of imide ring formation in the present invention include trimellitic anhydride, pyromellitic dianhydride, ethylene glycol bis anhydro trimellitate, and propylene glycol. Alkyl, such as bis-anhydro trimellitate, 1, 4- butanediol bis-an hydro trimellitate, hexamethylene glycol bis-an hydro trimellitate, polyethyleneglycol bis-an hydro trimellitate, polypropylene glycol bis-an hydro trimellitate, etc. Lenglycolbisanhydrotrimellitate, 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'-diphenylsulfontetracarboxylic dianhydride, m-terphenyl-3,3', 4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride Water, 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 dianhydride, 1,3-bis (3,4-dicarboxy Phenyl) -1,1,3,3-tetramethyldisiloxane dianhydride etc. are mentioned, These may be used independently and may be used in combination of multiple.

As the acid component of the present invention, aliphatic or cycloaliphatic acid anhydrides or cycloaliphatic dicarboxylic acids can be used as other acid components to the extent that the effects of the present invention are not impaired other than the components (a) to (c) described above. It is available. For example, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, hexahydropyromellitic acid Dianhydrides, cyclohexa-1-ene-2,3,5,6-tetracarboxylic dianhydride, 3-ethylcyclohexa-1-ene-3- (1,2), 5,6-tetracarboxyl Acid dianhydride, 1-methyl-3-ethylcyclohexane-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexa-1-ene-3- ( 1,2), 5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1- (1,2), 3,4-tetracarboxylic dianhydride, 1-propylcyclohexane-1- ( 2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3), 3- (2,3) -tetracarboxylic dianhydride, dicyclo Hexyl-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'-tetracarboxyl Acid dianhydrides, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride Water, bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, hexahydrotrimellitic anhydride, cyclohexanedicarboxylic acid, and the like. It may be used alone or in combination of plural. It is preferable that these components are 20 mol% or less in an acid component from a heat resistant viewpoint of the polyamideimide resin obtained and the flame retardance of the adhesive resin composition using the same.

As diisocyanate or diamine which has an aromatic ring used by this invention, in diisocyanate, it is diphenylmethane-2,4'- diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4, for example. , 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'-di Isocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-di Methoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, di Phenylether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6 Dee Cyanate, m-xylylenediisocyanate, p-xylylenediisocyanate, naphthalene-2,6-diisocyanate, 4,4 '-[2,2-bis (4-phenoxyphenyl) propane] diisocyanate, 3 , 3 'or 2,2'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'- or 2,2'-diethylbiphenyl-4,4'-diisocyanate, 3,3'- Dimethoxy biphenyl-4,4'- diisocyanate, 3,3'- diethoxy biphenyl-4,4'- diisocyanate, etc. are mentioned, As diamine, the diamine corresponding to these diisocyanate is mentioned, These may be used independently and may be used in combination of multiple.

An aliphatic or alicyclic structure can be used as the isocyanate or amine component to the extent that the effects of the present invention are not impaired. For example, diisocyanate or diamine which hydrogenated any one of the components mentioned in the preceding claim can be used. Moreover, isophorone diisocyanate, 1, 4- cyclohexane diisocyanate, 1, 3- cyclohexane diisocyanate, 4,4'- dicyclohexyl methane diisocyanate, ethylene diisocyanate, propylene diisocyanate, hexamethylene diisocyanate, and Diamine corresponding to these etc. are mentioned.

In the polyamideimide resin of the present invention, it is possible to copolymerize a compound having three or more functional groups for the purpose of improving heat resistance. For example, hydroxyl groups, such as dicarboxylic acid, such as polyfunctional carboxylic acid, such as trimesic acid, and hydroxyl groups, such as 5-hydroxyisophthalic acid, and dicarboxylic acid, which has amino groups, such as 5-aminoisophthalic acid, glycerin, polyglycerol, etc. And those having three or more amino groups such as tris (2-aminoethyl) amine. Among these, dicarboxyl having hydroxyl groups such as 5-hydroxyisophthalic acid in terms of reactivity and solubility. It is preferable to have 3 or more amino groups, such as an acid and a tris (2-aminoethyl) amine, and the quantity is 20 mol% or less with respect to an acid component or an amine component. When it exceeds 20 mol%, a crosslinking point may increase, and it may gelatinize at the time of polyamide manufacture, or generate an insoluble matter.

In the polyamideimide resin of the present invention, polyester is used as a flexible and adhesiveness imparting component other than acrylonitrile-butadiene rubber and aliphatic dicarboxylic acid having 4 to 12 carbon atoms to the extent that the effect of the present invention is not impaired. , Polyether, polycarbonate, dimer acid, polysiloxane and the like can be used. In that case, since the effect of this invention, such as heat resistance, solubility, and adhesiveness, may be impaired when there are many copolymerization amounts to polyamideimide resin, these components are preferably 10 mol% or less with respect to all the acid component or the amine component. Do.

As a method of obtaining the polyamideimide resin of this invention, the method of manufacturing from an acid component and an isocyanate component (isocyanate method), or the method of ring-closing after making an acid component react with an amine component ( Direct method) or a known method such as reacting a compound having an acid anhydride and an acid chloride with a diamine. Industrially, the isocyanate method is advantageous.

The polymerization of the polyamideimide resin is obtained by dissolving and heating the acid component and the isocyanate or amine component in a solvent. At this time, it is preferable that the ratio of an acid component and an isocyanate or amine component is 100: 91-100: 109. If it is out of this range, the molecular weight does not increase sufficiently, and there is a possibility that the mechanical strength is insufficient or gelates during polymerization. Moreover, it is preferable that the imide ring part of the polyamide-imide resin obtained by this invention is 90% or more ring-closed in view of resin and resin varnish stability. For that purpose, it is necessary to fully react at the time of superposition | polymerization of polyamideimide resin, and there exists a method of making reaction temperature high or adding a catalyst.

As a solvent which can be used for superposition | polymerization of the polyamideimide resin of this invention, N-methyl- 2-pyrrolidone, (gamma) -butyrolactone, dimethyl imidazolidinone, dimethyl sulfoxide, dimethylformamide, N-ethyl, for example 2-pyrrolidone, dimethylacetamide, cyclohexanone, cyclopentanone, tetrahydrofuran, etc. are mentioned, Among these, since a boiling point is low and the polymerization efficiency is good, dimethylacetamide is preferable. Moreover, after superposition | polymerization, it can dilute with the solvent used for superposition | polymerization or another low boiling point solvent, and can adjust a non volatile matter concentration and a solution viscosity.

As the low boiling point solvent, aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane, heptane and octane, alcohol solvents such as methanol, ethanol, propanol, butanol and isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, Ketone solvents such as cyclohexanone and cyclopentanone, ether solvents such as diethyl ether and tetrahydrofuran, and ester solvents such as ethyl acetate, butyl acetate and isobutyl acetate.

Furthermore, alkali metals such as sodium fluoride, potassium fluoride and sodium methoxide, triethylenediamine, triethylamine, diethanolamine, 1,8-diazabicyclo [5,4,0] -7- in order to promote the reaction Amines such as undecene and 1,5-diazabicyclo [4,3,0] -5-nonene and catalysts such as dibutyltin dilaurate can be used.

2. Polyamideimide Resin Composition

The polyamide-imide resin solution obtained by this invention can add a thermosetting component and can be used as an adhesive agent (thermosetting resin composition). When using the said thermosetting resin composition as an adhesive agent, in order to make drying temperature low and to prevent hardening reaction from advancing at the time of drying, it is preferable that the resin solution contains the low boiling point solvent with good dryability. As a low boiling point solvent suitable for an adhesive agent (thermosetting resin composition), ethanol, toluene, xylene, methyl ethyl ketone, etc. are mentioned, In order to discover the superiority in drying property, 60 mass of one or more types of solvents chosen from these group are selected. It is preferable that 10 mass% or more of polyamide-imide resins melt | dissolve in the mixed solvent which contains 40 mass of dimethylacetamide. By having this solubility, not only is it excellent in dryness, but when it adds a thermosetting component and it is set as an adhesive agent (thermosetting resin composition), it is not insolubilized by the solvent of a thermosetting component, and also time-lapse stability as a thermosetting resin composition, Excellent storage stability.

The dissolution in the present invention means that the solution is kept in a 25 ° C. atmosphere and the solid is not precipitated for 24 hours or more, and the viscosity rise of the solution during that time is less than 1.5 times.

When the polyamideimide resin obtained by the present invention is used in a printed wiring board, particularly a flexible printed wiring board requiring flexibility, the polyamideimide resin has a logarithmic viscosity of 0.2 dl / g or more and a glass transition temperature of 80. It is preferable that tensile modulus is less than 2000 Mpa by more than degreeC. When the logarithmic viscosity is less than 0.2 dl / g, the molecular strength of the polyamideimide resin is low, so that the mechanical strength may be a problem. When the glass transition temperature is less than 80 ° C, the heat resistance of the polyamideimide resin is insufficient. When the tensile modulus is 2000 MPa or more, the resin may be hard and brittle, so that the adhesive strength is low, and when curling occurs in the coating or the substrate in the coating or drying process. There is.

As a thermosetting component which can be used for the thermosetting resin composition using the polyamideimide resin obtained by this invention, an epoxy resin, an isocyanate compound, a melamine resin, a cyanate compound, a phenol resin, a maleimide compound, etc. are mentioned, Among these, The epoxy compound is preferable from the physical properties and workability of the cured coating film. Examples of the epoxy resin include hydrogenated bisphenol A type epoxy resins such as bisphenol A type epoxy resins such as JER828 and 1001 manufactured by Japan Epoxy Resin Co., Ltd., brand names ST-2004 and 2007 manufactured by Toto Kasei Co., Ltd. Bisphenol F-type epoxy resins, such as the brand name YDF-170, 2004, and brand names of brominated bisphenol A type epoxy resins, such as the brand name YDB-400 and 600 of Toto Kasei Co., Ltd., Japan Epoxy Resin Co., Ltd. product name jER152, 154, Nippon Kayaku Co., Ltd. brand name EPPN-201, BREN, Dow Chemical company brand name DEN-438, such as phenol novolak-type epoxy resin, Toto Kasei Co., Ltd. brand name YDCN-702, 703 Flexible epoxy resins, such as o-cresol novolak-type epoxy resins, such as brand name EOCN-125S, 103S, and 104S by Nippon Kayaku Co., Ltd., and brand name YD-171 by Toto Kasei Co., Ltd., DIC Corporation Cyclopenta such as HP-7200, HP-7200H of the production Epoxy resin having a Yen skeleton, trade name Epon1031S manufactured by Yuka Shell Epoxy Co., Ltd., trade name Araldite 0163, manufactured by Chiba Specialty Chemicals, Ltd., trade name Denacol EX-611, manufactured by Nagase Chemtex Co., Ltd. Multifunctional epoxy resin, such as 614, EX-622, EX-512, EX-521, EX-421, EX-411, EX-321, Yuka Shell Epoxy Co., Ltd. brand name Epicoat 604, Toto Kasei Co., Ltd. Brand name YH-434 of manufacture, brand name of TETRAD-X, TETRAD-C of Mitsubishi Gas Chemical Co., Ltd., brand name GAN of Nippon Kayaku Co., Ltd. brand name ELM-120 of Sumitomo Kagaku Co., Ltd. production Heterocyclic containing epoxy resins, such as amine type epoxy resin, brand name Araldite PT810 of Chiba Specialty Chemicals Co., Ltd., brand name Celoxide 2021 of Daicel Kagaku Kogyo Co., Ltd., EHPE3150, ERL4234 of UCC company make Alicyclic epoxy resin, Dainippon ink Kagaku Kogyo Co., Ltd. brand name Epiclone E Bixylenol type epoxy resins, such as bisphenol S-type epoxy resins, such as XA-1514, triglycidyl isocyanurate, such as TEPIC by Nissan Chemical Industries, Ltd., and brand name YX-4000 by Yuka Shell Epoxy Co., Ltd. And bisphenol-type epoxy resins such as trade name YL-6056 manufactured by Yuka Shell Epoxy Co., Ltd. may be used, and these may be used alone or in combination of two or more thereof.

Among these epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins having more than two epoxy groups in one molecule, o-cresol novolac type epoxy resins, and amine type epoxy resins are non- It is halogen type and is preferable at the point of the compatibility with the polyamideimide resin obtained by this invention, solvent resistance, chemical resistance, and moisture resistance improvement.

The solvent solution of the polyamideimide resin and the epoxy resin of this invention is excellent in adhesiveness, and can firmly adhere | attach a polyimide film and copper foil. The obtained copper polyimide film laminated body is excellent in solder heat resistance, and when used as a coverlay on a circuit, it is excellent in insulation reliability (migration resistance). This is because in the polyamideimide resin obtained by copolymerizing acrylonitrile-butadiene rubber and aliphatic dicarboxylic acid having 4 to 12 carbon atoms in a specific range, introduction of aliphatic groups increases solvent solubility and Since the chain length is neither short nor long, and properly dispersed in the polyamideimide, the adhesion by acrylonitrile-butadiene rubber, the flexibility of aliphatic dicarboxylic acid, and the introduction of a high polar amide group, It is thought that adhesiveness improves synergistically.

The thermosetting resin composition using the polyamideimide resin of this invention can add the hardening | curing agent and hardening accelerator of an epoxy resin in the range which does not impair a characteristic. Although there will be no restriction | limiting in particular if it is a compound reacting with an epoxy resin, For example, an amine type hardening | curing agent, the compound which has a phenolic hydroxyl group, the compound which has a carboxylic acid, the compound which has an acid anhydride, etc. are mentioned. The curing catalyst is not particularly limited as long as it promotes the reaction between the epoxy resin, the polyamideimide resin and the curing agent. For example, Shikoku Kasei Kogyo Co., Ltd., 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- Imidazole derivatives such as OK, 2P4MHZ, 2PHZ, 2P4BHZ, guanamines such as acetoguanamine and benzoguanamine, diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicydi Polyamines such as andamides, urea, urea derivatives, melamine, polybasic hydrazides, organic acid salts and / or epoxy adducts thereof, amine complexes of boron trifluoride, ethyldiamino-S-triazine, 2,4- Triazine derivatives such as diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine, trimethylamine, triethanolamine, N, N-dimethyl jade Amine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, DBU (1,8-diazabicyclo Tertiary amines such as [5,4,0] -7-undecene), DBN (1,5-diazabicyclo [4,3,0] -5-nonene), organic acid salts thereof and / or tetraphenyl Organic phosphines such as boronate, polyvinylphenol, polyvinylphenol bromide, tributylphosphine, triphenylphosphine, tris-2-cyanoethylphosphine, and tri-n-butyl (2,5-di Quaternary phosphonium salts such as hydroxyphenyl) phosphonium bromide, hexadecyltributylphosphonium chloride, tetraphenylphosphonium tetraphenylboronate, quaternary ammonium salts such as benzyltrimethylammonium chloride, phenyltributylammonium chloride, The polycarboxylic anhydride, diphenyl iodonium tetrafluoroboronate, triphenylsulfonium hexafluoro antimony Cationic polymerization, such as ethylene, 2,4,6-triphenylthiopyryllium hexafluorophosphate, Irgacure 261 (manufactured by Chiba Specialty Chemicals), Optomer SP-170 (manufactured by ADEKA) And equimolar reactants of a catalyst, styrene-maleic anhydride resin, phenyl isocyanate and dimethylamine, and an equimolar reactant of organic polyisocyanate such as tolylene diisocyanate and isophorone diisocyanate and dimethylamine. These hardening agents and hardening accelerators may be used independently, or may be used in combination of 2 or more types.

An inorganic or organic filler can be added to the thermosetting resin composition using the polyamideimide resin of this invention in the range which does not impair a characteristic. Examples of the 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 ), and barium titanate (BaOTiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbOTiO 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 ), yttrium-containing zirconia (Y ₂ O ₃ -ZrO ₂ ), barium silicate (BaO · 8SiO 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) and the like can be used, and these may be used alone or in combination of two or more thereof. You may also In the case of adding these fillers, since the work process of dispersion | distribution is needed, and the flexibility and workability which the resin composition originally had may be impaired depending on the use using the resin composition of this invention, When adding, it is preferable to adjust the kind of filler to be used and the quantity to add.

A flame retardant can be added to the thermosetting resin composition using the polyamideimide resin of this invention in the range which does not impair a characteristic. It is preferable that a flame retardant is non-halogen type from consideration to an environment, and as a non-halogen-type flame retardant used by this invention, what is necessary is just to melt | dissolve in said polyamideimide resin composition, Although there is no restriction | limiting in particular, Hydrolysis resistance and heat resistance In terms of preventing bleeding out of the flame retardant on the surface of the coating film, phosphazenes and phosphinic acid derivatives are preferable. You may use these individually or in combination of 2 or more types.

Examples of phosphazenes include cyclic cyanophenoxyphosphates such as cyclic phenoxyphosphazenes such as the brand name SPE-100 manufactured by Otsuka Chemical Co., Ltd. and FP-300 manufactured by Fushimi Seiyakusho Co., Ltd. Cyclic hydroxyphenoxy phosphazenes, such as Zen and the Otsuka Chemical Co., Ltd. brand name SPH-100, A chain phenoxy phosphazene, a crosslinked phenoxy phosphazene, etc. are mentioned, but a chain force Since pazene has a substituent at the terminal of the molecule, phosphorus content generally decreases as compared with cyclic phosphazene. Therefore, in this invention, cyclic phosphazene is preferable and cyclic trimer and / or tetramer phosphazene is more preferable.

In the case of non-reactive phosphazene, bleeding occurs on the surface over time, or the phosphorus of glass is eluted due to hydrolysis under excessive use conditions, or the insulating property is degraded by the decomposition product. Most preferably, reactive phosphazene having a functional group reacting with the epoxy resin is selected. Specifically, cyclic hydroxyphenoxy phosphazene etc. which have a hydroxyl group are mentioned.

Examples of phosphinic acid derivatives include, for example, HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and HCA-HQ (10- (2,5-dihydroxy) manufactured by Sanco Co., Ltd. Phenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide), 10- (2,5-dihydroxynaphthyl) -10-hydro-9-oxa-10-phosphaphenan Tren-10-oxide, BCA (10-benzyl-10-hydro-9-oxa-10-phosphazanthrene-10-oxide), phenylphosphinic acid, diphenylphosphinic acid, and the like.

In addition to the non-halogen-based flame retardants described above, other non-halogen-based flame retardants may be used in combination if necessary within a range that does not impair low warpage, heat resistance, and bleed. Examples thereof include phosphorus-containing epoxy resins copolymerized with HCA skeleton, phosphorus-containing polyester resins, and condensed phosphate esters such as resorcil diphenyl phosphate. However, the present invention is not limited thereto, and may be used in combination of two or more thereof.

3. Flame Retardant Adhesive Composition

The flame-retardant adhesive composition of this invention contains (A) polyamideimide resin, (B) phosphorus containing epoxy resin, and (C) phosphorus compound, and phosphorus content rate with respect to the total mass of (A)-(C) component is 2.0 mass It is characterized by the above-mentioned.

(A) polyamideimide resin

The polyamideimide resin (A) used in the present invention is the aforementioned polyamideimide resin, which is a polyamideimide resin obtained by reacting an acid component of the following (a) to (c) with a diisocyanate or diamine having an aromatic ring. When the total acid component of the polyamideimide resin is 100 mol%, the proportion of each acid component is (a) 3 mol% to 10 mol%, (b) 10 mol% to 80 mol%, (c) 10 Mole% to 87 mole%:

(a) acrylonitrile-butadiene rubber having carboxyl groups at both ends,

(b) aliphatic dicarboxylic acids having 4 to 12 carbon atoms,

(c) Acid anhydrides of polycarboxylic acids having an aromatic ring

The polyamide-imide resin (A) can be used as an adhesive (thermosetting resin composition) by adding a thermosetting component to form a solvent solution. When using the said thermosetting resin composition as an adhesive agent, in order to make a drying temperature low and to prevent a hardening reaction from advancing too much at the time of drying, it is preferable that the resin solution contains the low boiling point solvent with good dryability. As a low boiling point solvent suitable for an adhesive agent (thermosetting resin composition), ethanol, toluene, xylene, methyl ethyl ketone, etc. are mentioned, In order to discover the superiority in drying property, 60 mass of one or more types of solvents chosen from these group are selected. It is preferable that 10 mass% or more of polyamide-imide resins melt | dissolve in the mixed solvent containing% or more.

By having this solubility, it is excellent not only in drying property but also the following (B) phosphorus containing epoxy resin, (C) phosphorus compound, (D) epoxy resin hardening | curing agent, and (E) epoxy resin which does not contain phosphorus, (F ) When a silane coupling agent or the like is added to form an adhesive (thermosetting resin composition), the stability over time and the storage stability as the thermosetting resin composition are excellent.

The dissolution in the present invention means that the solution is kept in a 25 ° C. atmosphere and the solid is not precipitated for 24 hours or more, and the viscosity rise of the solution during that time is less than 1.5 times.

As for the polyamide-imide resin in this invention, it is preferable that logarithmic viscosity is 0.2 dl / g or more, glass transition temperature is 80 degreeC-200 degreeC, and tensile modulus is less than 2000 Mpa. When the logarithmic viscosity is less than 0.2 dl / g, the molecular strength of the polyamideimide resin is low, so that the mechanical strength may be a problem. When the glass transition temperature is less than 80 ° C, the heat resistance of the polyamideimide resin is insufficient. When the tensile modulus is 2000 MPa or more, the resin may be hard and brittle, so that the adhesive strength is lowered, and curling in the coating or drying process may be a problem. Moreover, when glass transition temperature becomes larger than 200 degreeC, when joining a to-be-adhered body as a flexible printed wiring board, the heat lamination (thermocompression bonding) temperature for fully bonding will become high, productivity, workability will fall, and solvent solubility will be inferior. Falls.

(A) polyamideimide resin in this invention is melt | dissolved in a solvent with the following (B)-(F) component, is excellent in adhesiveness as a flame-retardant adhesive composition, and adheres a polyimide film and copper foil firmly. can do. The obtained copper polyimide film laminated body is excellent in solder heat resistance, and when used as a coverlay on a circuit, it is excellent in insulation reliability (migration resistance). This is because in the polyamideimide resin obtained by copolymerizing acrylonitrile-butadiene rubber and aliphatic dicarboxylic acid having 4 to 12 carbon atoms in a specific range, introduction of aliphatic groups increases solvent solubility and Since the chain length is neither short nor long and properly dispersed in the polyamideimide, the adhesiveness is synergistically due to the adhesion of acrylonitrile-butadiene rubber, the flexibility of aliphatic dicarboxylic acid, and the introduction of a highly polarized amide group. It is thought that sex is improved.

(B) Phosphorus-containing epoxy resin

The phosphorus-containing epoxy resin (B) used in the present invention is an epoxy resin having a phosphorus atom as a chemical bond by using a reactive phosphorus compound, and may be one having two or more epoxy groups in one molecule, and a bisphenol-A epoxy resin and a bisphenol Hydrogenated F type epoxy resin, bisphenol S type, or these, Glycidyl ether type epoxy resins, such as a phenol novolak-type epoxy resin and a cresol novolak-type epoxy resin, hexahydrophthalic acid glycidyl ester, and dimer acid Glycidyl ester epoxy resins such as glycidyl esters, glycidylamine epoxy resins such as triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, epoxidized polybutadiene, epoxidized soybean oil, etc. Linear aliphatic epoxy resins and the like.

Moreover, as a reactive phosphorus compound used for a phosphorus containing epoxy resin, 9,10- dihydro-9-oxa-10- phosphofanthrene-10-oxide (manufactured by Sanko Co., Ltd., brand name: HCA), 10 -(2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphazphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name: HCA-HQ), and the like, and the like are mentioned above. A phosphorus containing epoxy resin is obtained by reacting with one epoxy resin. As these commercial items, Epiclon EXA9710 (made by DIC Corporation, phosphorus content rate: 3 mass%), EXA9748 (made by DIC Corporation, phosphorus content rate: 4.5 mass%), FX305 (manufactured by Toto Kasei Co., Ltd., phosphorus Content rate: 3 mass%) etc. are mentioned.

The compounding quantity of the phosphorus containing epoxy resin used by this invention is 1 mass part-200 mass parts with respect to 100 mass parts of (A) polyamideimide resin, Preferably it is 3 mass parts-160 mass parts, More preferably, It is 5 mass parts-120 mass parts, More preferably, they are 10 mass parts-80 mass parts. When the phosphorus-containing epoxy resin is less than 1 part by mass, the flame retardancy is inferior, and when the phosphorus-containing epoxy resin is more than 200 parts by mass, the heat resistance and the adhesiveness are inferior, and the mechanical strength is lowered, whereby cracking tends to occur when the sheet shape is formed.

(C) phosphorus compounds

Although the phosphorus compound (C) used by this invention is not specifically limited, A phosphazene and a phosphinic acid derivative are preferable at the point of hydrolysis resistance, heat resistance, and bleed-out. You may use these individually or in combination of 2 or more types.

The phosphazene compound is represented by the following general formula (1) or (2) (wherein X is the same or different and represents hydrogen, a hydroxyl group, an amino group, an alkyl group, an aryl group, an organic group, and as the organic group, for example, an alcohol group, a phenoxy group, an allyl) Group, cyanophenoxy group, hydroxyphenoxy group, etc., n is an integer of 3-25.

Examples of commercially available products of these phosphazenes include cyclic phenoxyphosphazene (manufactured by Otsuka Chemical Co., Ltd., trade name: SPB-100, SPE-100), cyclic cyanophenoxyphosphazene (manufactured by Fushimi Seiyakusho Co., Ltd.). Trade name: FP-300), cyclic hydroxyphenoxy phosphazene (manufactured by Otsuka Chemical Co., Ltd., brand name: SPH-100), and the like.

In addition, the addition type phosphazene may cause bleeding out over time, elute the phosphorus of glass under the influence of hydrolysis, etc. under excessive use conditions, and the electrical insulation may fall. Therefore, preferably, reactive phosphazene having a functional group reacting with the epoxy resin is selected. Specifically, cyclic hydroxyphenoxy phosphazene etc. which have phenolic hydroxyl group are mentioned.

As the phosphinic acid derivative, a phenanthrene type phosphinic acid derivative is preferable, for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanco Co., Ltd., brand name: HCA), 10-benzyl-10-hydro-9-oxa-10-phosphazphenanthrene-10-oxide (manufactured by Sanco Co., Ltd., brand name: BCA), and the like.

Of the phosphinic acid derivatives described above, HCA has reactivity with an epoxy resin, but may cause bleed-out and inferior high temperature and high humidity resistance, so that the compounding amount is appropriately selected in consideration of performance.

In addition to the above-described phosphorus compounds, other phosphorus compounds may be used alone or in combination of two or more as necessary in a range that does not impair flame retardancy, solder heat resistance and bleed-out.

The phosphorus content rate in the flame-retardant adhesive composition of this invention is 2.0 mass%-5.0 mass%, Preferably it is 2.2 mass%-4.5 mass%, More preferably, it is 2.5 mass%-4.0 mass%. When phosphorus content rate is less than 2.0 mass%, favorable flame retardance is not obtained and when it exceeds 5.0 mass%, heat resistance, adhesiveness, and electrical insulation tend to fall.

(D) epoxy resin curing agent

The epoxy resin curing agent (D) used in the present invention is not particularly limited as long as it is usually used as a curing agent for epoxy resins. As this (D) epoxy resin hardening | curing agent, a polyamine type hardening | curing agent, an acid anhydride type hardening | curing agent, a boron trifluoride amine complex salt, a phenol resin etc. are mentioned, for example. Examples of the polyamine curing agent include diethylenetriamine, tetraethylenetetramine, tetraethylenepentamine, isophoronediamine, diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone and dicyandie. Polyamines such as amides, urea, urea derivatives, melamine, polybasic hydrazide, organic acid salts and / or epoxy adducts thereof, and the like. Examples of the acid anhydride curing agent include phthalic anhydride, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, and cyclobutanetetracarboxylic acid. Dianhydride, hexahydropyromellitic dianhydride, cyclohexa-1-ene-2,3,5,6-tetracarboxylic dianhydride, 3-ethylcyclohexa-1-ene-3- (1,2) , 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexa -1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1- (1,2), 3,4-tetracarboxylic dianhydride, 1 -Propylcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3), 3- (2,3) -tetra Carboxylic acid dianhydride, dicyclohexyl-3,4,3 ', 4'-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride , 1-propylcyclo Acid-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3), 3- (2,3) -tetracarboxylic acid Dianhydrides, 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] octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, Hexahydro trimellitic anhydride etc. are mentioned. The said hardening | curing agent may be used individually by 1 type, and may use 2 or more types together.

(D) The compounding quantity of an epoxy resin hardening | curing agent is 0 mass%-5 mass%, when the whole non volatile matter of a flame-retardant adhesive composition is 100 mass%, Preferably it is 0 mass%-3 mass%. When the compounding quantity exceeds 5 mass%, there exists a tendency for heat resistance to fall.

(E) Epoxy resin which does not contain phosphorus

The epoxy resin which does not contain the phosphorus (E) used by this invention will not be specifically limited if it is an epoxy resin which does not contain the phosphorus atom in the molecule | numerator. The epoxy resin may be modified with silicone, urethane, polyimide, polyamide, or the like, and may contain sulfur atoms, nitrogen atoms, and the like in the molecular skeleton.

Examples of such epoxy resins include glycidyl ethers such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type, or hydrogenated compounds thereof, phenol novolak type epoxy resins, and cresol novolak type epoxy resins. Glycidyl amines such as glycidyl ester-based epoxy resins such as epoxy resins, hexahydrophthalic acid glycidyl esters, and dimer acid glycidyl esters, triglycidyl isocyanurate, and tetraglycidyl diaminodiphenylmethane Linear aliphatic epoxy resins, such as an epoxy resin, epoxidized polybutadiene, and epoxidized soybean oil, etc. are mentioned. Examples of such commercially available products include hydrogenated bisphenol A type epoxy resins such as bisphenol A type epoxy resins such as JER828 and 1001 manufactured by Japan Epoxy Resin Co., Ltd., and brand names ST-2004 and 2007 manufactured by Toto Kasei Co., Ltd. Phenolic novolac-type epoxy resins, such as bisphenol F-type epoxy resins, such as brand name YDF-170 of 2004, the brand name JER152 of Japan epoxy resin, Ltd. make, brand name DEN-438 by Dow Chemical Co., Ltd. Brand name YDCN-702, 703 of Kasei Co., Ltd. brand name EOCN-125S, 103S, 104S of Nippon Kayaku Co., Ltd. o-cresol novolak-type epoxy resins, such as 104S, brand name HP-7200 of DIC Co., Ltd. product , Epoxy resin having a cyclopentadiene skeleton such as HP-7200H, flexible epoxy resin such as YD-171 manufactured by Toto Kasei Co., Ltd., trade name Epon1031S manufactured by Yuka Shell Epoxy Co., Ltd., Chiba Specialty Chemicals Co., Ltd. Product name Y multifunctional epoxy such as 0163, Nagase Chemtex Co., Ltd. product name Denacol EX-611, EX-614, EX-622, EX-512, EX-521, EX-421, EX-411, EX-321 Resin, brand name Epicoat 604 of Yuka Shell Epoxy Co., Ltd., brand name YH-434 of Toto Kasei Co., Ltd., brand name TETRAD-X, TETRAD-C of Mitsubishi Gas Chemical Co., Ltd., Nippon Kayaku Co., Ltd. Heterocyclic containing epoxy resins, such as amine-type epoxy resins, such as ELM-120, the brand name of Sumitomo Chemical Co., Ltd., brand name Araldite PT810 of Chiba Specialty Chemicals, Inc. Bisphenol S type epoxy resins, such as cycloaliphatic epoxy resins, such as Celoxide 2021, EHPE3150, and UCC Co., Ltd. make, and the brand name Epiclolon EXA-1514 by DIC Corporation, Nissan Chemical Co., Ltd. Triglycidyl isocyanurate, such as TEPIC of Kogyo Co., Ltd., brand name YX-40 of Yuka Shell Epoxy Co., Ltd. product Bixphenol-type epoxy resins, such as 00, a bisphenol-type epoxy resin, such as a brand name YL-6056 by Yuka Shell Epoxy Co., Ltd., etc. are mentioned, You may use these individually by 1 type or in combination of 2 or more types.

(E) The compounding quantity of the epoxy resin which does not contain phosphorus is 0 mass%-20 mass%, when the whole non volatile matter of a flame-retardant adhesive composition is 100 mass%, Preferably it is 0 mass%-15 mass%. When the compounding quantity exceeds 20 mass%, there exists a tendency for sufficient flame retardance to not be obtained.

(F) silane coupling agent

The (F) silane coupling agent used in the present invention is not particularly limited as long as it is a conventionally known silane coupling agent as an adhesion imparting agent, and specific examples thereof include aminosilane, mercaptosilane, vinylsilane, epoxysilane, methacrylsilane and isocyanate. Silane, ketimine silane or a mixture or reactant thereof, or a compound obtained by the reaction of these with a polyisocyanate.

Examples of such silane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldiethoxysilane and bistrimethoxysilylpropylamine. , Bistriethoxysilylpropylamine, bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- ( Aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylethyldiethoxysilane, etc. Aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropylethyldie Mercaptosilanes such as oxysilane, vinyltrimethoxysilicone Vinylsilanes such as vinyltriethoxysilane and tris- (2-methoxyethoxy) vinylsilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylethoxysilane and γ-glyci Doxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Epoxy silanes such as silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. Isocyanate silanes such as methacryl silane, isocyanate propyl triethoxy silane and isocyanate propyl trimethoxy silane, ketimin silane such as ketiminated propyl trimethoxy silane and ketiminated propyl triethoxy silane, and the like. Species alone, again Two or more kinds may be used in combination.

Among these silane coupling agents, epoxy silanes have reactive epoxy groups, and thus react with (A) polyamideimide resins, (B) phosphorus-containing epoxy resins, (D) epoxy resin curing agents, and (E) epoxy resins that do not contain phosphorus. Since it is possible to do this, it is preferable at the point of heat resistance and moisture-heat resistance improvement.

(F) The compounding quantity of a silane coupling agent is 0 mass%-3 mass%, when the whole non volatile matter of a flame-retardant resin composition is 100 mass%, Preferably it is 0 mass%-2 mass%. When the compounding quantity exceeds 3 mass%, there exists a tendency for heat resistance to fall.

It is preferable that all of the components (A) to (F) used in the present invention are dissolved in a solvent of any one of dimethylacetamide, ethanol, toluene, xylene, and methyl ethyl ketone at 25 ° C and a solid content concentration of 25% by mass. As a result, a uniform dispersion process such as a filler is not necessary, and problems such as economicality, non-uniformity, reduction in varnish usage period, and decrease in chemical resistance, which are the above-described problems, can be avoided.

Moreover, in this invention, a hardening accelerator can be used as needed. A hardening accelerator is used in order to accelerate reaction of an epoxy resin with the various components which can react with an epoxy resin, and if it does not contain a halogen atom, it will not specifically limit. As a hardening accelerator, tertiary amine, quaternary ammonium salt, phosphine, imidazole, octylate, etc. are mentioned, You may use individually by 1 type and may use 2 or more types together.

Although the fillers, such as an organic filler and an inorganic filler, and its dispersing agent can be added to the flame-retardant resin composition of this invention in the range which does not impair the characteristic, since the processability and performance of a printed wiring board may fall by adding, It is necessary to fully consider the use and the kind and quantity of the filler.

(A)-(F) component used for this invention is melt | dissolved in the organic solvent, and is used by adjusting the said composition as a solution. Examples of the organic solvent include dimethylacetamide, ethanol, methanol, toluene, xylene, methyl ethyl ketone, dimethylformamide, cyclohexanone, N-methyl-2-pyrrolidone, isopropanol, acetone, and the like. Examples thereof include dimethylacetamide, ethanol, toluene, xylene, and methyl ethyl ketone. These organic solvents may be used individually by 1 type, and may use 2 or more types together.

When melt | dissolving and using the said composition in the organic solvent, in order not to advance hardening reaction at the time of drying of a solvent, it is desired to make drying temperature low. Therefore, it is preferable that the resin solution contains many low boiling point solvents with favorable dryness. As a low boiling point solvent suitable for the solution of the said composition, ethanol, toluene, xylene, methyl ethyl ketone, etc. are mentioned, In order to discover an advantage in drying property, 50 mass% or more of 1 type of solvents chosen from these group are selected. It is preferable that the said composition melt | dissolves 30 mass% or more in the mixed solvent containing.

The total concentration (solid content concentration) of the components (A) to (F) in the adhesive solution is usually 10% by mass to 45% by mass, preferably 15% by mass to 40% by mass, and more preferably 20% by mass. % To 35% by mass. If this concentration is less than 10 mass%, the thickness of an adhesive will become thin, heat resistance and adhesive strength will fall, and when larger than 45 mass%, since the viscosity of a solution becomes too high, it becomes difficult to coat uniformly.

4. glue sheet

The adhesive sheet for electronic components of this invention means the thing of the structure which makes the flame-retardant adhesive composition of this invention an adhesive bond layer, and has at least 1 or more peelable protective film layers. For example, the two-layered constitution of the protective film layer / adhesive layer or the three-layered constitution of the protective film layer / adhesive layer / protective film layer corresponds to this. The protective film layer herein is not particularly limited as long as it can be peeled off without damaging the form of the adhesive layer. Examples thereof include polyethylene, polyester, polyolefin, polymethylpentene, polyvinyl chloride, polyvinylidene fluoride, polyphenylene sulfide, and the like. The plastic film of this invention, the film which carried out the coating process with silicone, a fluorine compound, etc., the paper which laminated these, the paper which impregnated or coated the peelable resin, etc. are mentioned. In addition, it is also possible to use metals, ceramics, and the like, and there is an advantage of providing new functions such as heat dissipation, electronic shielding, reinforcement, identification, as well as protection for the purpose of surface insulation and environmental resistance.

The manufacturing method of an adhesive sheet coats the adhesive solution which melt | dissolved the flame-retardant adhesive composition of this invention in the solvent to the above-mentioned film which has mold release property, The temperature of 50 degreeC-200 degreeC, Preferably it is 70 degreeC-160 degreeC, More preferably, Preferably, it dries at 100 to 130 degreeC for 2 to 10 minutes, and forms an adhesive bond layer. The thickness after drying of the said adhesive bond layer is 5 micrometers-40 micrometers, Preferably they are 10 micrometers-25 micrometers. Moreover, when it is set as a three-layered constitution, further, a mold release protective film is laminated and laminated | stacked.

5. coverlay film

The coverlay film of this invention makes the flame-retardant adhesive composition of this invention an adhesive bond layer, and includes the two-layered constitution of an insulating plastic film layer / adhesive layer, or the three-layered constitution of an insulating plastic film layer / adhesive layer / protective film layer. do. The insulating plastic film is a film having a thickness of 5 μm to 200 μm containing plastics such as polyimide, polyester, polyphenylene sulfide, polyether sulfone, polyether ether ketone, aramid, polycarbonate, polyarylate, and the like. You may laminate | stack the some film chosen from. What was demonstrated as a protective film of the adhesive sheet mentioned above can be used for a protective film.

The manufacturing method of a coverlay film coats the adhesive solution which melt | dissolved the flame-retardant adhesive composition of this invention in the solvent to the above-mentioned insulating plastic film, and is 50 degreeC-200 degreeC, Preferably it is 70 degreeC-160 degreeC, More preferably, Is dried at 100 to 130 ° C. for 2 to 10 minutes to form an adhesive layer. The thickness after drying of the said adhesive bond layer is 5 micrometers-40 micrometers, Preferably they are 10 micrometers-25 micrometers. In addition, when it is set as a three-layer structure for storage etc., further, a mold release protective film is laminated and laminated | stacked.

6. Flexible printed wiring board

The flexible printed wiring board of this invention makes the flame-retardant adhesive composition of this invention an adhesive bond layer, and says the thing of the structure which bonded the insulating plastic film and copper foil with the said adhesive layer. For example, the flexible printed wiring board which has the said adhesive bond layer formed on one side or both surfaces of an insulating film, and the 1 or 2 layer copper foil to which the said adhesive bond layer of one layer or two layers was adhere | attached is mentioned. The said copper foil can use the rolled copper foil and electrolytic copper foil conventionally used for a flexible printed wiring board. The insulating plastic film can use what was demonstrated as the insulating plastic film of the coverlay film mentioned above.

The manufacturing method of a flexible printed wiring board coats the adhesive solution which melt | dissolved the flame-retardant adhesive composition of this invention in the solvent to the above-mentioned insulating plastic film, The temperature of 50 degreeC-200 degreeC, Preferably it is 70 degreeC-160 degreeC, More preferably, Is dried at 100 to 130 ° C. for 2 to 10 minutes to form an adhesive layer. The thickness after drying of the said adhesive bond layer is 5 micrometers-40 micrometers, Preferably they are 10 micrometers-25 micrometers. Subsequently, a laminated body is obtained by arrange | positioning copper foil on an adhesive bond layer and heat-laminating at the temperature of 80 degreeC-150 degreeC, Preferably 110 degreeC-130 degreeC. The polyamide-imide resin used in the present invention cannot be thermally compressed well if the Tg is high in terms of heat resistance and the lamination temperature is lower than 100 ° C., but if it is higher than 150 ° C., workability tends to be lowered. The laminate is further cured by heating at 120 ° C to 200 ° C, preferably at 140 ° C to 170 ° C to completely cure the adhesive, thereby obtaining a flexible printed wiring board.

Even if the flexible printed wiring board obtained by this invention is immersed for 30 second in the solder bath of 330 degreeC, it can exhibit the solder heat resistance excellent so that neither external abnormality, such as peeling, swelling, and discoloration, may generate | occur | produce. In addition, even after leaving for 24 hours in an atmosphere of 40 ° C and a relative humidity of 90% and absorbing moisture, even after being immersed in a solder bath at 300 ° C for 30 seconds, all of the solder heat resistance such as peeling, swelling, and discoloration do not occur. Was not easily achieved in the prior art.

Example

In order to demonstrate this invention further in detail, an Example is given to the following, but this invention is not limited to an Example at all.

1. About polyamideimide resin and its resin composition

The characteristic of resin in the Example was measured and evaluated by the following method.

Logarithmic viscosity

The solution which melt | dissolved 0.5 g of dry solid polymer in 100 ml of NMP was measured at 30 degreeC using the Uberode viscosity tube.

Tensile Modulus

The obtained polyamideimide resin solution was applied onto a copper foil so as to have a film thickness of 20 µm after drying, dried at 150 ° C. for 10 minutes with a hot air dryer, and then dried at 200 ° C. for 5 hours with an inert oven. The copper foil was etched and removed to prepare a polyamideimide resin film, to form a strip having a width of 10 mm from these films, and measured at a tensile rate of 20 mm / min using tensilon manufactured by Toyo Baldwin. .

(Glass transition temperature)

The same polyamide-imide resin film used for the measurement of the tensile modulus of elasticity was measured using a dynamic viscoelasticity measuring apparatus DVA-220 manufactured by Haiti Keisoku Seiko Co., Ltd. It was.

(Soluble)

The same polyamide-imide resin film used for measuring the tensile modulus was dissolved in a solvent in which 40 parts by mass of dimethylacetamide and 60 parts by mass of toluene were mixed so that the nonvolatile content was 10% by mass. In the 25 degreeC atmosphere, the solution was transparent and the state which does not precipitate solid was kept for 24 hours, and what melt | dissolved completely was made into (circle) and the thing which was not ×.

(Adjustment of adhesive resin composition)

To 100 g of the obtained polyamideimide resin solution, 50 g of a toluene solution having a nonvolatile content of 30% by mass of an epoxy resin (jER152, a phenol novolac epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.) and 4,4'-diaminodiphenyl sulfone 4 g of methyl ethyl ketone solution of 15 mass% of non volatile matters (SEIKACURE-S by Wakayama Seika Co., Ltd.) was added, and the adhesive resin composition was obtained.

(Adhesive strength)

The adhesive resin composition was apply | coated to the polyimide film (Apical NPI) whose thickness is 25 micrometers so that the film thickness after drying might be 15 micrometers, and the solvent was dried at 130 degreeC for 5 minutes with the hot air dryer. Then, it bonded together at 130 degreeC and the process surface of the electrolytic copper foil (USLP by Nippon Denkai Co., Ltd. thickness of 18 micrometers), and hardened | cured by heating at 170 degreeC for 3 hours.

Subsequently, the obtained copper clad laminated board was cut | disconnected to 1.0 mm width, 90 degree peeling was carried out at the tensile speed of 50 mm / min using tensilon by Toyo Baldwin Co., Ltd. at room temperature, and peeling strength was measured.

(Solder heat resistance)

The state when the copper clad laminated board which measured the adhesive force was floated in the 300 degreeC solder bath for 60 second was observed. (Circle) and thing other than that which did not have peeling and swelling were made into x.

(Insulation Reliability: Migration Resistance)

A comb pattern (circuit) having a line thickness of 50 µm was prepared on a two-layer CCL (trade name VYLOFLEX) manufactured by Toyobo Co., Ltd., washed with 3% hydrochloric acid, and then washed with water. The adhesive resin composition was apply | coated whole surface on the obtained circuit so that the film thickness after drying might be set to 20 micrometers, and the adhesive bond layer was heat-hardened on 170 degreeC and the conditions for 180 minutes. Thereafter, a DC voltage of 50 V was applied, and the value of the insulation resistance after 500 hr exceeded 1 × 10 ⁸ Ω was lower than that of the lower one, or the dendrite was observed between the wirings.

Example 1 (polyamideimide resin 1):

In a four-necked separate flask equipped with a stirrer, a cooling tube, a nitrogen inlet tube and a thermometer, 105.67 g (0.55 mol) of trimellitic anhydride, 80.09 g (0.40 mol) of sebacic acid, and acrylics having both ends of the carboxylic acid 175 g (0.05 mol) of ronitrile butadiene rubber (CTBN 1300 x 13, number average molecular weight 3500, acrylonitrile portion ratio 26 wt%), 252.75 g (1.0 mol) of 4,4'-diphenylmethane diisocyanate, dimethyl 526 g of acetamide was added, the temperature was raised to 100 ° C under a nitrogen stream, and the mixture was allowed to react for 2 hours. Subsequently, 117 g of dimethylacetamide was added, followed by reaction at 150 ° C for 5 hours, followed by dilution by addition of 439 g of toluene and 146 g of dimethylacetamide, and cooling to room temperature to give a brown but not turbid polyamideimide. Resin solution 1 was obtained.

Table 1 shows the results obtained by measuring the logarithmic viscosity, the glass transition temperature, and the tensile modulus of the polymer obtained from the resin solution.

In addition, as mentioned above, the adhesive resin composition was prepared from the polyamide-imide resin solution, the copper clad laminated board was manufactured using the said adhesive resin composition, and the adhesive strength and solder heat resistance were evaluated about the said copper clad laminated board. Moreover, the migration resistance which is a necessary characteristic as a coverlay was evaluated by the method of the preceding paragraph. The obtained results are shown in Table 1.

Example 2 (polyamideimide resin 2):

In a four-necked two-liter flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, 142.18 g (0.74 mol) of trimellitic anhydride, 40.45 g (0.20 mol) of sebacic acid, and acrylonitrile having carboxylic acid at both ends Add 210.0 g (0.06 mol) of butadiene rubber (CTBN 1300 × 13), 125.13 g (0.5 mol) of 4,4'-diphenylmethane diisocyanate, 87.08 g (0.5 mol) of tolylene diisocyanate, 517 g of dimethylacetamide, It heated up to 100 degreeC under nitrogen stream, and made it react for 2 hours. Subsequently, after making it react at 150 degreeC for 5 hours, 431 g of toluene and 258 g of dimethylacetamide were added and diluted, and it cooled to room temperature, and obtained the brown but not turbid polyamide-imide resin solution 2.

Table 1 shows the measurement results and evaluation results obtained in the same manner as in Example 1.

Example 3 (polyamideimide resin 3):

In a four-necked 2-liter flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer, 105.67 g (0.55 mol) of trimellitic anhydride, 92.12 g (0.4 mol) of dodecane diacid, and acryl with carboxylic acid at both ends 175 g (0.05 mol) of nitrile butadiene rubbers (CTBN 1300 × 13), 250.25 g (1.0 mol) of 4,4'-diphenylmethane diisocyanate and 535 g of dimethylacetamide were added thereto, and the temperature was raised to 100 ° C. under a nitrogen stream. The reaction was carried out for 2 hours. Subsequently, after making it react at 150 degreeC for 5 hours, 594 g of toluene and 119 g of dimethylacetamide were added and diluted, and it cooled to room temperature, and obtained the brown but not turbid polyamide-imide resin solution 3.

Table 1 shows the measurement results and evaluation results obtained in the same manner as in Example 1.

Example 4 (polyamideimide resin 4):

In a four-necked two-liter flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube and a thermometer, 105.67 g (0.55 mol) of trimellitic anhydride, 58.46 g (0.4 mol) of adipic acid, and acrylo with both ends of the carboxylic acid 175 g (0.05 mol) of nitrile butadiene rubbers (CTBN 1300 × 13), 250.25 g (1.0 mol) of 4,4'-diphenylmethane diisocyanate and 501 g of dimethylacetamide were added thereto, and the temperature was raised to 100 ° C. under a nitrogen stream. The reaction was carried out for 2 hours. Subsequently, after making it react at 150 degreeC for 5 hours, 418 g of toluene and 251 g of dimethylacetamide were added and diluted, and it cooled to room temperature, and obtained the brown but not turbid polyamide-imide resin solution 4.

Table 1 shows the measurement results and evaluation results obtained in the same manner as in Example 1.

Example 5 (polyamideimide resin 5):

In a four-necked separate flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer, 67.25 g (0.35 mol) of trimellitic anhydride, 121.34 g (0.60 mol) of sebacic acid, and acrylonitrile butadiene rubber having both ends of carboxylic acid (CTBN 1300 × 13) 175 g (0.05 mol), 252.75 g (1.0 mol) of 4,4'-diphenylmethane diisocyanate, 526 g of dimethylacetamide were added thereto, and the temperature was raised to 100 ° C under a nitrogen stream, followed by reaction for 2 hours. I was. Furthermore, after making it react at 150 degreeC for 5 hours, 438 g of toluene and 263 g of dimethylacetamides were added and diluted, and it cooled to room temperature, and obtained the brown but not turbid polyamideimide resin solution 5.

Table 1 shows the measurement results and evaluation results obtained in the same manner as in Example 1.

Comparative Example 1 (Polyamideimide Resin 6):

In a four-necked separate flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer, 89.15 g (0.58 mol) of trimellitic anhydride, 64.72 g (0.40 mol) of sebacic acid, and acrylonitrile butadiene rubber having both ends of carboxylic acid (CTBN 1300 × 13) 56 g (0.02 mol), 201.2 g (1 mol) of 4,4'-diphenylmethane diisocyanate, 423.31 g of dimethylacetamide were added thereto, and the temperature was raised to 100 ° C under a nitrogen stream, followed by reaction for 2 hours. I was. Subsequently, after making it react at 150 degreeC for 5 hours, 353 g of toluene and 212 g of dimethylacetamides were added and diluted, and it cooled to room temperature, and obtained the brown but not turbid polyamideimide resin solution 6.

Table 1 shows the measurement results and evaluation results obtained in the same manner as in Example 1.

Comparative Example 2 (Polyamideimide Resin 7):

In a four-necked separate flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer, 172.92 g (0.90 mol) of trimellitic anhydride, 10.11 g (0.05 mol) of sebacic acid, and acrylonitrile butadiene rubber having both ends of carboxylic acid (CTBN 1300 × 13) 175 g (0.05 mol), 4,4'-diphenylmethane diisocyanate 247.75 g (0.99 mol) and 518 g of dimethylacetamide were added thereto, and the temperature was raised to 100 ° C under a nitrogen stream to react for 2 hours. I was. Subsequently, after making it react at 150 degreeC for 5 hours, 431 g of toluene and 259 g of dimethylacetamide were added and diluted, and it cooled to room temperature, and obtained the brown polyamide-imide resin solution 7, but was turbid.

Table 1 shows the measurement results and evaluation results obtained in the same manner as in Example 1.

Comparative Example 3 (Polyamideimide Resin 8):

In a four-necked separate flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, 9.61 g (0.05 mol) of trimellitic anhydride, 182.02 g (0.90 mol) of sebacic acid, and acrylonitrile butadiene rubber having both ends of carboxylic acid (CTBN 1300 × 13) 175 g (0.05 mol), 252.75 g (1.0 mol) of 4,4'-diphenylmethane diisocyanate, 529 g of dimethylacetamide were added thereto, and the temperature was raised to 100 ° C under a nitrogen stream, followed by reaction for 2 hours. I was. Furthermore, after making it react at 150 degreeC for 5 hours, 441 g of toluene and 264 g of dimethylacetamide were added and diluted, and it cooled to room temperature, and obtained the brown but not turbid polyamideimide resin solution 8.

Table 2 shows the measurement results and evaluation results obtained in the same manner as in Example 1.

Comparative Example 4 (Polyamideimide Resin 9):

In a four-necked separate flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer, 105.67 g (0.55 mol) of trimellitic anhydride and 175 g of acrylonitrile butadiene rubber (CTBN 1300 × 13) having carboxylic acid at both ends ( 0.05 mol), Eisakoic acid (manufactured by Okamura Yushi Co., Ltd.) 137 g (40 mol), 125.13 g (0.5 mol) of 4,4'-diphenylmethane diisocyanate, 87.08 g (0.5 mol) tolylene diisocyanate, dimethylacetamide 542g was put, it heated up to 100 degreeC under nitrogen stream, and made it react for 2 hours. Subsequently, after making it react at 150 degreeC for 5 hours, 452 g of toluene and 271 g of dimethylacetamide were added and diluted, and it cooled to room temperature, but since the solubility of the polyamideimide resin was insufficient and the resin solution was remarkably turbid, Subsequent measurement results and evaluation were stopped.

Comparative Example 5 (polyamideimide resin 10):

In a four-necked separate flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer, acrylonitrile butadiene rubber having 86.4 g (0.45 mol) of trimellitic anhydride, 80.09 g (0.40 mol) of sebacic acid, and carboxylic acid at both ends (CTBN 1300 × 13) 525 g (0.15 mol), 252.75 g (1.0 mol) of 4,4'-diphenylmethane diisocyanate, 854 g of dimethylacetamide were added thereto, and the temperature was raised to 100 ° C under a nitrogen stream to react for 2 hours. I was. Subsequently, 190 g of dimethylacetamide was added, followed by reaction at 150 ° C for 5 hours, followed by dilution by addition of 712 g of toluene and 237 g of dimethylacetamide, followed by cooling to room temperature to give a brown, slightly cloudy polyamideimide resin solution. 10 was obtained.

Table 2 shows the measurement results and evaluation results obtained in the same manner as in Example 1.

Comparative Example 6 (Polyamideimide Resin 11):

In a four-necked separate flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer, 175 g of acrylonitrile butadiene rubber (CTBN 1300 × 13) having 182.4 g (0.95 mol) of trimellitic anhydride and carboxylic acid at both ends ( 0.05 mol), 252.75 g (1.0 mol) of 4,4'- diphenylmethane diisocyanate, and 519 g of dimethylacetamides were put, it heated up to 100 degreeC under nitrogen stream, and made it react for 2 hours. Subsequently, 115 g of dimethylacetamide was added and the mixture was reacted at 150 ° C for 5 hours. Then, 433 g of toluene and 144 g of dimethylacetamide were added and diluted, and the mixture was cooled to room temperature to give a brown polyamideimide resin solution 11. Got it. The solution looked slightly cloudy.

Table 2 shows the measurement results and evaluation results obtained in the same manner as in Example 1.

Comparative Example 7 (polyamideimide resin 12):

175 g of acrylonitrile butadiene rubber (CTBN 1300 × 13) having 91.2 g (0.475 mol) of trimellitic anhydride and carboxylic acid at both ends in a four-necked separate flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer ( 0.05 mole), 81.7 g (0.475 mole) of 1,4-cyclohexanedicarboxylic acid, 222 g (1.0 mole) of isophorone diisocyanate, 1,8-diazabicyclo [5,4,0] -7-unde 1.52 g (0.01 mol) of sen and 482 g of dimethylacetamide were put, it heated up to 100 degreeC under nitrogen stream, and made it react for 2 hours. Furthermore, after making it react at 150 degreeC for 5 hours, 241 g of dimethylacetamides and 402 g of toluene were added and diluted, and it cooled to room temperature, and obtained the yellow and non-turbid polyamide-imide resin solution 12.

Table 2 shows the measurement results and evaluation results obtained in the same manner as in Example 1.

As mentioned above, the polyamideimide which introduce | transduced the C4-C12 aliphatic component and acrylonitrile butadiene rubber component in the specific range not only improves the solubility to the low boiling point solvent of a polyamideimide, but also has remarkable adhesiveness. It turns out that the adhesive composition of this invention is excellent in solder heat resistance and migration resistance, and is suitable for the use of a printed wiring board.

On the other hand, in the comparative example 1, since there are few acrylonitrile butadiene rubber components, adhesiveness and solder heat resistance are bad, in comparative example 2, since there are few aliphatic components, solubility and adhesiveness are bad and resin performance is not exhibited. In the comparative example 3, since there are many aliphatic components and also an amide component, the water absorption of resin becomes high, migration resistance is bad, and in comparative example 4, since the aliphatic chain length is too long, comparative example 5 In, since there are too many acrylonitrile butadiene rubber components, in Comparative Example 6, since it does not have a C4-C12 aliphatic component, solubility is remarkably bad, respectively. In Comparative Example 7, there is a disadvantage in that the reactivity is low, and solubility is improved when the alicyclic component can be introduced, but the adhesion is inferior and migration resistance is poor.

2. About flame retardant resin composition, adhesive sheet, coverlay film and flexible printed wiring board

The measured value described in the Example is measured by the following method. In addition, what is simply part in an Example shows a mass part.

Logarithmic viscosity

The solution which melt | dissolved 0.5 g of dry solid polymer in 100 ml of NMP was measured at 30 degreeC using the Uberode viscosity tube.

Tensile Modulus

The obtained polyamideimide resin solution was applied onto the copper foil so that the film thickness after drying was 20 µm, dried at 150 ° C. for 10 minutes with a hot air drier, and then dried at 200 ° C. for 5 hours in an inert oven to etch the copper foil. By removing, the polyamide-imide resin film was created, the strip of 10 mm width was made from these films, and it measured by 20 mm / min of tensile velocity using tensilon of Toyo Baldwin.

<Glass transition temperature>

The same polyamide-imide resin film used for the measurement of the tensile modulus of elasticity was measured using a dynamic viscoelasticity measuring apparatus DVA-220 manufactured by Haiti Keisoku Seiko Co., Ltd. It was.

Solubility

In the solvent which mixed 40 mass parts of dimethylacetamides, and 60 mass parts of 1 type of solvents chosen from the group which consists of ethanol, toluene, xylene, and methyl ethyl ketone, the same polyamide-imide resin film used for the measurement of a tensile elasticity modulus, It dissolves so that a non volatile matter may be 10 mass%. It was left to stand in a 25 degreeC atmosphere for 24 hours, and it investigated whether the solution was transparent and whether the solid substance precipitated.

(Judgment) (circle): The solution is transparent and melt | dissolved completely without precipitation of a solid.

       X: The thing which did not melt | dissolve, or the precipitation of solid thing was seen

<Synthesis Examples 1-5 of Polyamide-imide Resin, Comparative Synthesis Examples 1-6>

In the same manner as in Example 1, Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 6 of the polyamide-imide resin were prepared. Table 3 shows physical property values and characteristic evaluation results of the polyamide-imide resin thus obtained.

<Various components of adhesive composition>

(B) Phosphorus-containing epoxy resin

  (1) EXA-9710: A methyl ethyl ketone melted product (non-volatile content concentration 70 mass%) of Dic Corporation's phosphorus-containing epoxy resin (epoxy equivalent: 490, phosphorus content: 3.0 mass%)

(C) phosphorus compounds

  (1) HCA: Sanco Co., Ltd. phenanthrene type organic phosphate compound, 9,10-dihydro-9-oxa-10-phosphafaphenanthrene-10-oxide (phosphorus content: 14.3 mass%)

  (2) BCA: Sanco Co., Ltd. phenanthrene type organic phosphate compound, 10-benzyl-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (phosphorus content: 10.1 mass%)

  (3) SPH-100: Otsuka Chemical Co., Ltd. cyclic hydroxyphenoxy phosphazene (phosphorus content: 12.5 mass%)

(D) epoxy resin curing agent

  DDS: 4,4'-diaminodiphenylsulfone

(E) Epoxy resin which does not contain phosphorus

  jer152: Japan epoxy resin Co., Ltd. phenol novolak type epoxy resin (epoxy equivalent 175)

(F) silane coupling agent

  KBM-403: Shin-Etsu Chemical Co., Ltd. 3-glycidoxypropyl trimethoxysilane (epoxy equivalent 283)

<Example 6>

Said various components were added to the solution of (A) polyamide-imide resin obtained by the synthesis example 1, and the solution of the adhesive composition 1 of Example 6 was obtained.

That is, in a glass bottle, 173.3 parts of the solution of the polyamideimide resin (A) obtained by the synthesis example 1, 22.9 parts of EXA-9710, 64.0 parts of the dimethylacetamide solution of 25 mass% of non volatile matter concentrations of BCA, and SPH- 20.0 parts of methyl ethyl ketone solution of 100 mass% of non volatile matter concentrations, 12.0 parts of toluene solution of 50 mass% of non volatile matter contents of jER152, 20.0 parts of methyl ethyl ketone solution of 15 mass% of non volatile matter concentrations of DDS, KBM- 5.0 parts of toluene solutions of 20 mass% of non-volatile matter concentrations of 403, and 16.1 parts of dilution solvents (dimethylacetamide / toluene = 20/80) were put, and the adhesive composition solution of Example 6 of 30 mass% of non volatile matter concentrations was obtained. In Table 4, the compounding ratio of solid content which made the total solid content 100 mass% is shown.

Using the adhesive solution obtained in Example 6, an adhesive sheet, a coverlay film, and a flexible printed wiring board were manufactured. These manufacturing methods are shown below.

<Adhesive sheet>

The adhesive composition obtained in Example 6 was applied onto a polyester film subjected to a release treatment so as to have a thickness of 25 占 퐉 after drying, and dried in a blowing oven at 130 ° C. for 3 minutes to give an uncured or semi-cured adhesive. Sheets were prepared.

<Coverlay film>

The solution of the adhesive composition obtained in Example 6 was applied onto a 25 μm polyimide film (manufactured by Kaneka Co., Apical 25 NPI) so as to have a thickness of 25 μm after drying, followed by a blowing oven at 130 ° C. for 3 minutes. It dried inside and produced the coverlay film of the uncured or semi-hardened state.

<Flexible Printed Wiring Boards>

The solution of the adhesive composition obtained in Example 6 was applied onto a 25 μm polyimide film (manufactured by Kaneka Co., Ltd., Apical 25 NPI) so as to have a thickness of 16 μm after drying, followed by a blowing oven at 130 ° C. for 3 minutes. It dried inside to produce a film with an adhesive in an uncured or semi-cured state. The roughened surface of the adhesive coating surface and the electrolytic copper foil (18 micrometers in thickness, USLP by Nippon Denkai Co., Ltd.) or the rolled copper foil (18 micrometers in thickness, BHY manufactured by Nikko-Kinjoku Co., Ltd.) of the film in which the adhesive agent was obtained in this way was carried out (note ) A thermocompression bonding was performed under conditions of a lamination temperature of 130 ° C., a pressure of 3 MPa and a time of 20 seconds using a Nasec Corporation vacuum press laminate machine. By further heat-hardening this at 170 degreeC for 3 hours, the flexible printed wiring board was created.

The adhesive sheet, coverlay film, and flexible printed wiring board obtained as mentioned above were evaluated in accordance with the evaluation items as shown below.

<Peel strength>

In accordance with JIS C6471, a circuit having a pattern width of 1 mm was formed on the flexible printed wiring board, and the copper foil was placed in the 90 ° direction of the wiring board in a 50 mm / min direction at 25 ° C using RTM100 manufactured by Toyo Baldwin Co., Ltd. The tensile test was done at the tensile speed, and 90 degree peeling strength was measured.

(Decision) ◎: 15 N / cm or more

       ○: 11 N / cm or more less than 15 N / cm

       Δ: 6 N / cm or more but less than 11 N / cm

       ×: less than 6 N / cm

Solder Heat Resistance

(1) Normal state: According to JIS C6471, a test piece was created by cutting the said flexible printed wiring board into the square of 25 mm on one side, and the test piece was immersed for 30 second in the solder bath of 300 degreeC or more. The temperature at which no external appearance abnormalities such as peeling, swelling, and discoloration occurred in the test piece occurred.

(Judgment) (double-circle): 330 degreeC or more

       ○: 300 ° C or more and less than 330 ° C

       ×: less than 300 ° C

(2) Hygroscopicity: The test piece prepared in the same manner as in the above-described normal state was left for 24 hours in an atmosphere of 40 ° C and 90% relative humidity, and then the test piece was quickly immersed in a solder bath of 280 ° C or higher for 30 seconds. The temperature at which no external appearance abnormalities such as peeling, swelling, and discoloration occurred in the test piece occurred.

(Decision) (double-circle): 300 degreeC or more

       ○: 280 ° C or more and less than 300 ° C

       X: less than 280 degreeC

<Flammability>

The solution of the adhesive composition obtained in Example 6 was applied to both surfaces of a 12.5 μm polyimide film (manufactured by Kaneka Co., Apical 12.5 NPI) so as to have a thickness of 16 μm after drying, respectively, at 130 ° C. for 3 minutes, After drying in a ventilation oven, the sample was created by heat-hardening at 170 degreeC for 3 hours. Flame retardance was evaluated based on the UL-94VTM flame retardance standard.

(Judgment) (double-circle): It is equivalent to UL94 VTM-0, and the combustion of the sample piece was less than half.

       (Circle): It was UL94 VTM-0, and the combustion of the sample piece was more than half.

       ×: Do not satisfy UL94 VTM-0

<Insulation Reliability: Migration Resistance>

On the two-layer CCL (brand name Viroflex) by Toyobo Corporation, a comb pattern of 70 µm between lines was prepared. Apply the solution of the adhesive composition obtained in Example 6 to 25 micrometers on this circuit so that the thickness after drying may be set to 25 micrometers, and it is made to dry at 130 degreeC for 3 minutes, and then heat-cured at 170 degreeC for 3 hours, and a coverlay is installed. One sample was prepared. Thereafter, a direct current voltage of 50 V was applied under conditions of a temperature of 85 ° C. and a relative humidity of 85% to measure migration resistance.

(Judgment) (circle): The insulation resistance value after 500 hr exceeds 1x10 <^8> ohms, and the growth of dendrites is not seen.

X: When insulation resistance value after 500 hr was less than 1x10 <^8> ohms, or growth of dendrites was seen

Peel Strength after PCT Treatment

After the said flexible printed wiring board was cut | disconnected so that the sample width might be set to 5 mm, the sample was produced, and the PCT test was performed for 40 hours under the conditions of temperature 121 degreeC, 100% of humidity, and 2 atmospheres of atmospheric pressure using the autoclave by a Tomi Seiko company. In accordance with JIS C6471, using a Toyo Baldwin Corporation RTM100, a copper foil was subjected to a tensile test at a tensile rate of 50 mm / min in a direction of 90 ° of the wiring board in a 25 ° C atmosphere, and the 90 ° peeling strength was measured. It was.

(Decision) ◎: 10 N / cm or more

       ○: 6 N / cm or more less than 10 N / cm

       (Triangle | delta): 4 N / cm or more and less than 6 N / cm

       ×: less than 4 N / cm

Table 4 and Table 5 show the results obtained by the respective evaluation methods described above.

<Examples 7-13, Comparative Examples 8-16>

Similarly to the flame-retardant adhesive composition of Example 6, various components (B) to (F) were blended using the solutions obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 6 of the (A) polyamideimide resin, The flame-retardant adhesive composition of Examples 7-13 and Comparative Examples 8-16 which adjusted to the non volatile matter concentration 30% with the dilution solvent (dimethylacetamide / toluene = 20/80) was obtained. The compounding ratio of solid content which made the total solid content 100 mass% about each obtained adhesive composition is shown in Table 4 and Table 5. In addition, various components (B)-(F) were previously melt | dissolved in the solvent and used as a solution. The non-volatile content concentration and solvent composition of various components (B) to (F) are shown below.

HCA: 25% by mass of nonvolatile matter, dimethylacetamide solution

BCA: Non-volatile matter concentration of 25% by mass, dimethylacetamide solution

SPH-100: Non-volatile matter concentration 30% by mass, methyl ethyl ketone solution

DDS: 15% by mass of nonvolatile matter, methyl ethyl ketone solution

jER152: Non-volatile matter concentration 50% by mass, toluene solution

KBM-403: Non-Volatile Concentration 20% by Mass, Toluene Solution

In the same manner as in Example 6, the adhesive compositions of Examples 7 to 13 and Comparative Examples 8 to 16 were prepared, and an adhesive sheet, a coverlay film, and a flexible printed wiring board were produced and evaluated in the same manner as in Example 6. The results are shown in Tables 4 and 5.

As described above, the coverlay film and the flexible printed wiring board of the present invention are excellent in peel strength, solder heat resistance, flame retardancy and migration resistance, and excellent in the above characteristics even after treatment under high temperature and high humidity conditions. In particular, the solder heat resistance exhibits a very good characteristic that has not been conventionally able to withstand 330 ° C and can withstand 300 ° C even after moisture absorption, as shown in Examples 6 to 8 and 13.

The phosphorus content rate of the comparative example 8 is less than 2.0 mass%, out of the claim, and inferior to flame retardance.

The phosphorus content of the comparative example 9 is larger than 5.0 mass%, it is outside the claim, and it is inferior to solder heat resistance and migration resistance.

The comparative example 10 does not contain (B) phosphorus containing epoxy resin, it is outside the claim, and it is inferior to solder heat resistance, flame retardance, and migration resistance.

In Comparative Example 11, a polyamideimide resin outside the range of the claims of (b) aliphatic dicarboxylic acid having 4 to 12 carbon atoms is less than 10 mol%, and the peel strength is inferior.

In Comparative Example 12, a polyamideimide resin having a ratio of (b) aliphatic dicarboxylic acid having 4 to 12 carbon atoms outside the range of the claims of more than 80 mol% is used, and the solder heat resistance after moisture absorption is inferior.

In Comparative Example 13, (b) a polyamideimide resin outside the scope of claims using aliphatic dicarboxylic acid having more than 12 carbon atoms was used, and the peel strength was inferior.

Comparative Example 14 uses a polyamideimide resin having a ratio of (a) acrylonitrile-butadiene rubber having carboxyl groups at both ends of less than 3 mol%, and is inferior in peel strength.

In Comparative Example 15, the adhesiveness was remarkably inferior, and thermal bonding was not possible under the laminating conditions (temperature 130 ° C., pressure 3 MPa, time 20 seconds) of the flexible printed wiring board, and could not be evaluated.

In Comparative Example 16, (b) a polyamideimide resin outside the scope of claims not copolymerizing an aliphatic dicarboxylic acid having 4 to 12 carbon atoms was used, and the peel strength was inferior.

The polyamideimide resin of the present invention and the adhesive resin composition to which the thermosetting agent is added are useful for printed wiring boards such as copper clad laminates, coverlays, adhesive sheets, copper foils with resins, overcoat inks, prepregs, paints, As a coating agent etc., it can be used in the wide field of an electronic device.

In addition, the flame-retardant adhesive composition of the present invention is non-halogen, environmentally friendly, excellent in workability, and suitable for the production of flexible printed wiring boards. Moreover, the flame-retardant adhesive composition of this invention can be used as an insulating layer of an adhesive sheet, a coverlay film, a flexible printed wiring board, etc.

Claims (15)

A polyamideimide resin obtained by reacting a diisocyanate or diamine having an aromatic ring with an acid component of the following (a) to (c), each acid component when the total acid component of the polyamideimide resin is 100 mol%. Wherein the ratio of (a) 3 mol% to 10 mol%, (b) 10 mol% to 80 mol%, and (c) 10 mol% to 87 mol%:
(a) acrylonitrile-butadiene rubber having carboxyl groups at both ends,
(b) aliphatic dicarboxylic acids having 4 to 12 carbon atoms,
(c) Acid anhydride of polycarboxylic acid which has an aromatic ring. 10 mass% at 25 degreeC in the mixed solvent containing 60 mass of 1 or more types of solvents chosen from the group which consists of ethanol, toluene, xylene, and methyl ethyl ketone, and 40 mass of dimethylacetamides of Claim 1, Comprising: Polyamideimide resin which dissolves abnormally. The polyamideimide resin composition which added the thermosetting component to the polyamideimide resin of Claim 2. The polyamideimide resin composition according to claim 3, wherein the thermosetting component is an epoxy resin. The printed wiring board which used the polyamide-imide resin composition of Claim 3 or 4 as an adhesive agent. (A) polyamideimide resin, (B) phosphorus containing epoxy resin, (C) phosphorus compound, and (A) polyamideimide resin which has the acid component and aromatic ring of following (a)-(c) It is a polyamideimide resin obtained by making isocyanate or diamine react, and when the total acid component of the said polyamideimide resin is 100 mol%, the ratio of each acid component is (a) 3 mol%-10 mol%, (b) It is 10 mol%-80 mol%, (c) 10 mol%-87 mol%, The flame-retardant adhesive characterized by the phosphorus content rate with respect to the total mass of (A)-(C) component 2.0 mass%-5.0 mass%. Composition:
(a) acrylonitrile-butadiene rubber having carboxyl groups at both ends,
(b) aliphatic dicarboxylic acids having 4 to 12 carbon atoms,
(c) Anhydrides of polycarboxylic acids having an aromatic ring. The flame retardant adhesive composition of claim 6, wherein the compound (C) is a phosphazene and / or phosphinic acid derivative. The flame-retardant adhesive composition according to claim 6 or 7, further comprising (D) an epoxy resin curing agent. The flame-retardant adhesive composition of any one of Claims 6-8 which further contains the epoxy resin which does not contain (E) phosphorus. The flame-retardant adhesive composition according to any one of claims 6 to 9, further comprising (F) a silane coupling agent. The solid content concentration according to any one of claims 6 to 10, wherein all of the components (A) to (F) are 25 ° C in a solvent of any one of dimethylacetamide, ethanol, toluene, xylene, and methyl ethyl ketone. A flame retardant adhesive composition that dissolves at 25% by mass. The flame-retardant adhesive composition of any one of Claims 6-11 whose phosphorus content rate with respect to the total mass of the said (A)-(F) component is 2.0 mass%-5.0 mass%. An adhesive sheet comprising an adhesive layer and a peelable protective film layer laminated with the flame-retardant adhesive composition according to any one of claims 6 to 12, wherein the protective film layer is peelable on one or both sides of the adhesive layer. Having adhesive sheet. The coverlay film formed by laminating | stacking the adhesive bond layer and insulating plastic film layer containing the flame-retardant adhesive composition in any one of Claims 6-12. The flexible printed wiring board containing the insulating layer formed using the flame-retardant adhesive composition of any one of Claims 6-12.