TW201139589A - Coverlay film and circuit board - Google Patents

Abstract

This invention provides an adhesive resin composition which contains a polyimide resin having a group Ar (tetravalent aromatic group), a group R1 (divalent diaminosiloxane residual group), a group R2 (divalent aromatic diamine residual group), and a value of an index P of 0.7 or less, the index P representing the amount of polar groups contained in the composition calculated from the following formula (i) P value = {(A1+A2) / (B1+B2)} x 100...(i) wherein A1 = (number of the polar groups in group Ar) x (number of moles of group Ar), A2 = (number of the polar groups in group R2) x (number of moles of group R2), B1 = (molecular weight of group Ar) x (number of moles of group Ar), B2 = (molecular weight of group R2) x (number of moles of group R2), and wherein The numbers of the polar groups are: one for each of -X (hologen), -OH, -SH, -O-, -S-, -SO-, -NH-, -CO-, -CN-, -P=O, -OP-; two for each of -SO2-, -CONH-; and three for -SO3H.

Description

[Technical Field] The present invention relates to an adhesive resin composition useful as an adhesive on a circuit board such as a flexible printed wiring board and the like. [Prior Art] In recent years, with the progress of miniaturization, weight reduction, and space saving of electronic equipment, it is a flexible printed wiring board that is thin and lightweight, has bendability, and has excellent durability for repeated bending. The demand for (FPC, flexible printed ci rui ts) is increasing. Since FPC can be assembled in a space with a high degree of density in a limited space, it is not only used for wiring of movable parts of electronic equipment such as HDDs, DVDs, and mobile phones, but also for components such as cables and connectors. It is also continuing to expand. The FPC uses a cover film for the purpose of protecting the wiring portion. The cover film is formed by laminating a film for covering made of a synthetic resin such as a polyimide resin with an adhesive. In the production of the FPC, the cover film is adhered to the circuit board via an adhesive layer by, for example, hot pressing. In the subsequent layer, it is necessary to have high reproducibility for both the circuit wiring pattern and the covering film for copper wiring. As an adhesive for the cover film, it can be processed under a relatively low temperature hot pressing condition, and has excellent heat resistance and the like, and an adhesive resin composition for a printed circuit board is proposed (for example, Patent Document 1) In a mixed resin of a polyimine and an epoxy resin having a siloxane unit, one or more selected from the group consisting of a phosphate ester, a phthalate, a polyester, and a fatty acid ester A combination of plasticizers. In the case of an in-vehicle electronic device using an FPC in an automobile, it is repeated at a high temperature environment of about 150 ° C in a high-temperature environment of about 150 ° C. In the long-term use, the adhesion of the cover film and the wiring of the FPC is lowered, and the problem that the wiring protection function is greatly reduced is caused. With the expansion of the use of FPC, it is expected that not only in-vehicle electronic equipment will be used, but the use of FPC in the same severe temperature environment will increase in the future. Therefore, the FPC used in a high-temperature environment is strongly required to pay attention to the countermeasure against the reduction of the adhesion of the cover film. Accordingly, an object of the present invention is to provide an adhesive resin composition which can form an adhesive layer without deteriorating the adhesion between the wiring layer and the cover film in a high temperature environment. [Means for Solving the Problems] As a result of ascertaining the cause of the above problems, the present inventors have noticed that copper in the copper wiring diffuses into the adhesive layer of the cover film due to long-term use in a high-temperature environment. . Further, this copper diffusion is the main cause of the decrease in the adhesion force, and it has been found that the present invention can be completed by suppressing the diffusion of copper and maintaining good adhesion for a long period of time in a high temperature environment. That is, the adhesive resin composition of the present invention contains a polyimine which contains a constituent unit represented by the following general formulas (1) and (2). 5 322367 201139589 R1R2J i ΟΛΥΟ 、 , 'ArAr ΟΛΥΟ ΟΛΥΟ Ν Ν L Γ Γ Γ Γ 式 式 式 式 式 式 式 式 式 式 式 式 式 式 式 式 式 式 式 式 式 式 式 式 式 式 式 式 , , , , , , , , , , , , , , R2^f is a divalent aromatic diamine group of the genus, and m and n represent the respective structures; the molar ratio of the individual is in the range of 0 75 to 丨Q, and in the range of 0.25. Further, the p-value of the present adhesive resin composition is not more than 7.7. p , indicating the (4) index of the polar group contained in the composition, and according to the following number, P^ = {(AHA2)/(B1+B2)}x1〇〇", [here 'Al = ( The number of polar groups in the Ar group) x (A2 of the Ar group = (the number of polar groups in the RZ group) X (the number of moles of the R2 group),

Bl = (molecular weight of Ar group) x (molar number of Ar group) B2 = (molecular weight of R2 group) X (molar number of R2 group) The number of the aforementioned polar groups is: -X (X represents a tooth atom) , -OH, -SH, -〇-, ~s__ -CO CN---P=〇, -P〇- respectively as one, _S〇2-, -C0NH- as two, -S〇3H- As 3, and calculate]. NH-~S0- ' _ 322367 6 201139589 The above-mentioned polyimine resin of the adhesive resin composition of the present invention is obtained by using the above aromatic tetrafine and the above aromatic diamine having a P value of 1. G or less. It is better to be a supplement. The p value is an index indicating the amount of the polar group contained in the molecule, and is calculated from the following formulas (1)) and (iii). P value of aromatic tetracarboxylic anhydride = (Α1/β1)χ1〇〇...(ii) P value of aromatic diamine = (A2/B2)xl〇〇...(ii〇[here 'A Bu A2 m and B2 have the same meanings as described above. In the adhesive resin composition of the present invention, the P value of the aromatic diamine is preferably 7% or less. The adhesive resin composition of the present invention. In the above, the above-mentioned polyiminoimine is synthesized by using a diamine sulfoxane represented by the following general formula (3) as a raw material.

Rs r7 •(3) h2n—r3~_^ A 0_^丨卜r “NH2 R6 Rg [wherein R4R4 represents a divalent organic group which may also contain an oxygen atom, and L to 匕 respectively represent a carbon number of 丨 to 6 The hydrocarbon group, the average number of repetitions is 20%, and 8 mole % of the ruthenium main component. In the adhesive resin composition of the present invention, the molar ratio of the diamine sulfoxane of the above general formula (3) of all the raw materials is The adhesive resin composition of the present invention is a compound containing a plasticizer, and the index p value indicating the amount of the polar group contained in the composition is preferably 〇7 or less, and the value is based on the following formula: (iv) Calculated. '. 322367 7 201139589 P value={(A1+A2+A3)/(B1+B2+B3)}xl00 (iv) [here, A1, A2, B1, B2 are the same as above The meaning of A3 = (the number of polar groups in the plasticizer) x (the molar number of the plasticizer) B3 two (the molecular weight of the plasticizer) x (the molar number of the plasticizer), the number of polar groups is The adhesive resin composition of the present invention is preferably an adhesive for use as a cover film for protecting a wiring portion of a circuit board. The cover film of the present invention is laminated. a coating film for a coating layer and a coating film layer, and the adhesive layer is formed by using any of the above-described adhesive resin compositions. The circuit substrate of the present invention comprises a substrate and is formed on the substrate. The wiring layer and the cover film covering the wiring layer. The peel strength of the wiring layer and the cover film layer after the long-term heat resistance test at 150 ° C for 1000 hours in the air is 0.2 kN. [Effect of the invention] The adhesive resin composition of the present invention has a P value indicating a polar basis amount calculated by the formula (i) of 0.7 or less, even in a high temperature environment. It is also possible to form an adhesive layer which does not lower the adhesion to the metal wiring layer. Therefore, the adhesive resin composition of the present invention can improve the peeling strength of the formed cover film of the adhesive layer, and can improve the use of the cover film. [Embodiment] [Formation of the Invention] 8 322367 201139589 The present invention (4) is followed by a lyophilized mosquito comprising a polypyrene resin, the polyimine resin contained, The constituting sheet 70 represented by the general formulas (1) and (2). The polyimine resin is a thermoplastic resin, and the Ar group in the general formulae (1) and (2) is a tetravalent aromatic group derived from an aromatic __, R] group. It is a divalent diamine fluorenyl group derived from a diamine oxime, and a fluorenyl group is a divalent aromatic diamine group derived from an aromatic di. The presence of a constituent unit represented by the formula (1) in the resin The amount is in the range of 75 moles to (10) moles (10), and the enthalpy is in the range of 80 mole% to (10) mole%. The diamine oxime is removed by the diamine oxirane. The base of the amine-based oxime-bonded (Si-0-Si), by increasing the ratio of the oxy-oxygen bonding, the plasticizer can also impart sufficient flexibility to the adhesive layer without inhibiting the bonding. Cover the film's interesting bend. Further, since the plasticizer contains a large amount of polar groups, the advantage of not blending the plasticizer is exemplified by suppressing the amount of the polar group contained in the adhesive resin composition, and the P value can be lowered. Therefore, in the present invention, the value in the formula (1) is set to 0.75 or more: when the m value is less than 〇75, the effect of suppressing warpage cannot be sufficiently obtained. Further, by increasing the siloxane coupling, it is also believed that the effect of reducing the hardening shrinkage by reducing the imine bonding site of the polyimide resin. Due to these facts, the value of n of the formula (2) is set to 0 to 0 25 , and it is desirable to be in the range of 〇 to 〇 2. When the adhesive resin composition of the present invention is used as an adhesive for a cover film or the like, it is capable of maintaining an adhesive force in a high-temperature environment, and contains a polymerized unit represented by the above general formulas (1) and (2). The imine resin has a enthalpy value calculated according to the following formula (i): 7% or less, and preferably 〇. 6 or less. P value={(Al+A2)/(Bl+B2)}xl〇〇 • · · (i) 322367 9 201139589 [here,

Al = (the number of polar groups in the Ar group) x (the number of moles of the Ar group) A2 = (the number of polar groups in the R2 group) x (the number of moles of the R2 group)

Bl = (molecular weight of Af group) x (molar number of Ar group) B2 = (R2 based molecular weight) x (molar number of R2 group)]. This P value indicates an index of the amount of the polar group contained in the composition of the polyimide resin. The larger the P value, the larger the amount of the polar group contained in the composition containing the polyimide resin. When used as an adhesive for a cover film or the like, the polar group contained in the ruthenium layer serves to induce diffusion of copper from the copper wiring. That is, when a large amount of polar groups are contained in the adhesive layer, copper is widely diffused from the copper wiring into the adhesive layer in the reverse heating. As a result, the adhesion of the adhesive layer is weakened, and the cover film may become easily peeled off. In the adhesive resin composition of the present invention, by setting the P value to 0.7 or less (preferably 0.6 or less), the amount of the polar group contained in the composition is lowered to suppress the decrease in the adhesion force. . The polar group which is the basis for calculating the above P value is divided into three classes by the size of the electric dipole moment. The first class is -X (herein referred to as a halogen atom), -OH, -SH, -0---S---SO---NH---CO---CN, -P=0, -P0-, These are calculated as one polarity base. The second class is -S〇2-, -C0NH-, which are calculated as two polar groups. The third class is -S〇3-, which is calculated as a polar base. Then, as shown in the formula (i), the molar number and molecular weight of the aromatic tetracarboxylic anhydride group and the aromatic diamine group in the polyimine resin, and the above-mentioned polar groups contained in these groups The number can determine the P value. 10 322367 201139589 • In the adhesive resin composition of the present invention, the p value is calculated by containing the above-mentioned general formula (1), (2), the Ar group of the polyimine resin which constitutes the unit (aromatic tetracarboxylic anhydride) The reason why the polar group contained in the group (2) and the R2 group (aromatic diamine group) is used as a standard is that the amount of the polar group contained in the R group and the R2 group is approximately determined by the aggregation of the main component of the binder. The reason for the polarity of the entire imine resin. Therefore, the polar group contained in the R-group-containing diaminophosphonyl group and the polar group bonded to the quinone imine are not considered in calculating the P value. In the case of the above-mentioned P value, as the Ar group, for example, a group represented by the following formula (4) or formula (5) can be given.

[In the formula (5), W represents a 2-valent hydrocarbon group selected from a single bond, a divalent hydrocarbon group having 1 to 15 carbon atoms, _0_, _S-, -CO-, -S0_, _S02_, _NH_ or -C0NH_]. In particular, as the Ar group, in order to depress the P value, W in the formula (4) or the formula (5) is a single bond, a divalent hydrocarbon group having 1 to 15 carbon atoms, -S-, -C0- The group represented by the formula (4) or the formula (5) is preferably a single bond, a divalent hydrocarbon group having 1 to 15 carbon atoms, or a group represented by -C0-. Further, the constituent units represented by the above general formulas (1) and (2) may be present in a single polymer or may be a constituent unit of the copolymer. When a copolymer having a plurality of constituent units is present, it may be present as a block copolymer or as a random copolymer. The polyimine resin is generally produced by reacting an acid anhydride with a diamine. Therefore, the specific 11 322367 201139589 example of the polyimide resin can be understood by the description of the acid anhydride and the diamine. In the above general formulas (1) and (2), the 'Ar group can be said to be the base of the acid field, and the Ri group and the R2 group can be said to be the base of the diamine. Therefore, the ideal polyimine resin can be derived from an acid anhydride and a diamine. Description. However, the polyimine resin is not limited to those derived from an acid anhydride and a diamine as described herein. Examples of the anhydride having an Ar group include, for example, pyromellitic anhydride, 3'3''4,4'~2,3',4,4'-biphenyl tetracarboxylic. Dianhydride), 3, 3', 4, 4'-diphenylphosphonium tetracarboxylic dianhydride (3, 3', 4, 4, ~ (iiphenyl sulfone tetracarboxyl ic dianhydride), 4, 4,-oxydi-benzene 4,4'-oxydiphthalic anhydride is preferred. Also, as an acid anhydride, 2, 2, 3, 3'-, 2, 3, 3', 4'- or 3, 3, 4, 4, _ benzophenone tetracarboxylic dianhydride (2, 2', 3, 3'-, 2, 3, 3', 4, -〇!· 3, 3', 4, 4'-Benzophenone tetracarboxy1ic Dianhydride), 2, 3', 3, 4'-biphenyltetracarboxylic dianhydride, 2, 2', 3, 3,-biphenyltetracarboxylic dianhydride, 2, 3', 3, 4' - Benzoic acid, bis(2,3-dicarboxypheny 1)ether dianhydride, 3, 3' ', 4, 4' '-, 2, 3, 3' ', 4' ' - or 2, 2' ', 3, 3' ' - p-terphenyl tetracarboxylic dianhydride (3, 3' ', 4, 4' ' -, 2, 3 , 3' ',4',-or 2, 2 ,,3,3',-p- terpheylcarboxylic dianhydride), 2,2-bis(2,3- or 3,4-dicarboxyphenyl)-propane dianhydride, bis (2, 3- or 3, 4- Dicarboxyphenyl)methane dianhydride, bis(2,3- or 3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis(2,3- or 3,4-dicarboxyphenyl)B Alkane dianhydride, for example 1,2, 7, 8-, 1,2, 6, 7- or 1,2, 9, 10-phenanthrenecarboxylic acid dianhydride, 2, 3, 6, 7-nonanedicarboxylic acid Dihydride, 2,2-bis(3,4-dicarboxyphenyl) 12 322367 201139589 tetrafluoropropane dianhydride, 2, 3, 5, 6-cyclohexanedihydride, 2, 3, 6, 7-naphthalene Carboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, hydrazine, 4,5,8-naphthalenetetracarboxylic dianhydride, 4,8-dimercapto-1,2,3,5, 6, 7-hexahydronaphthalene_1,2,5,6-tetracarboxylic dianhydride, 2,6- or 2' 7-di-naphthalene-1,4,5, 8-tetracarboxylic dianhydride, 2 , 3, 6, 7-(or 1,4'5, 8-) tetra-naphthalene-1,4,5,8-(or 2,3, 6, 7-)tetracarboxylic dianhydride, 2, 3 , 8, 9-, 3' 4, 9' 10-, 4, 5, 10, 11- or 5, 6, 11, 12-fluorene tetracarboxylic dianhydride, cyclopentane-1, 2, 3, 4 -tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride Thiophene -2, 3, 4, 5-tetracarboxylic dianhydride, 4,4 '- bis (2,3-dicarboxy phenoxy) diphenyl dianhydride Yue dioxane. In addition, examples of the R2 group include the groups represented by the following formulas (6) to (8).

In the formulae (6) to (8), R9 is independently, and the i-calcinyl group 'z having a carbon number of 丨 to 6' represents a divalent hydrocarbon group having a single bond, carbon number i to i5, -0- , -S-, -, μ -2 r ^ ^ S〇2-, ~ΝΗ- or -CONH- the selected 2饧 group, the integers of the Sichuan table are not independent of each other, especially as the R2 base, In order to drive down p. Knot, =5: One is. The base = 〃 as a 1 group of diamine, for example, ",, diaminodiphenyl 322367 13 201139589 bond, 2' - methoxy- 4, 4'-diaminobenzimidil (2 ,1咐4'4'-diamin〇benZanilide), if bis(4_aminophenoxy)benzene, bis(4)aminophenoxy)benzene, 2,2,_bis[4_(4_amine Phenyloxy)phenyl]propane, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3, monodihydroxy-4,4'-diaminobiphenyl, 4 , 4'-diaminobenzimidamide, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, oxime [4_(4-aminophenoxy)phenyl] Bismuth, bis[4-(3-aminophenoxy)phenyl] hard, bis[4_(4-aminophenyloxy)]biphenyl, bis[4_(3-aminophenoxy)] Benzene, bis[(4)aminophenoxy)]biphenyl, bis[1-(3-aminophenoxy)]biphenyl, bis[4_(4-aminophenoxy)phenyl]methane, Bis[4-(3-aminophenyloxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl] Ether, bis[4-(4-aminophenoxy)]benzophenone, bis[4_(3-aminophenoxybenzophenone, bis[4,4'-(4-aminobenzene) Benzoquinone, bis[4,4, mono(3-aminophenoxy)]benzamide, 9,9-bis[4_(4-aminophenoxy)phenyl]indole 9,9-bis[4-(3-aminophenoxy)phenyl]indole, 2,2-bis-[4-(4-amine basic oxy)phenyl]hexafluoropropane, 2, 2-bis-[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-methylenedi-o-methylaniline, 4,4,-arylene-2'6 - dimethylaniline, 4, 4,-methylene-2,6-diethylaniline, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4, 4'-diaminodiphenylethane, 3,3,-diaminodiphenylethane, 4,4,-diaminodiphenylmethane, 3,3,-diaminodi Phenylmethane, 4,4,-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3,-amino group Diphenyl stone, 4, 4'-diaminodiphenyl test '3, 3'-diaminodiphenyl hydrazine, 3, 4'-diaminodiphenyl ether, benzidine, 3, 3 '-Diamine linkage 14 322367 201139589 Benzene, 3, 3'-dimethyl-4,4'-diaminobiphenyl, 3,3,-dimethoxybenzidine, 4-4' diamine Correct Biphenyl, 3, 3,, -diamino-p-terphenyl, m-phenylenediamine, p-phenylenediamine, 2,6-diamine, pyridinium, 1,4-bis(4-aminophenoxy) Benzene, 1'3-bis(4-aminophenoxy) stupid, 4,4,-[l,4-phenylene bis(l- again' group is represented by the following formula (3a) Methyl ethyl) ethyl diphenylamine, 4,4'-[l,3-phenylene bis(l-methylethylidene)]diphenylamine, bis(p-aminocyclohexyl)methane double —-Lu-Amino-tert-butylphenyl)-, bis(p-stone-methyl-mono-amino-benzyl)benzene, p-bis-decyl-4-aminebenzyl)benzene, p-pair (Μ_ Dimethyl-5-amine benzyl)benzene, anthracene, 5-monoamine naphthalene, 2,6-diamine naphthalene, 2,4-bis(wan-aminotributyl) benzene, 2, 4 Diaminotoluene, m-xylylene-2,5-diamine, p-xylylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,6-diamino Pyridine, 2' 5-monoamine ratio bit, 2, 5-diamino 3,4-oxadiazole, pyrazine, and the like.丨〇 丨〇 丨丨 R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R K K K K K K K K K K K K K K K K K K The average number of times of repetition T is the base of R1, in order to give the mR4 in the poly(5) a hydrocarbon group of 1 to 6 for JW, the average repeating diradical, R5 to "the carbon number of Atm is 5 to The basis of 15 is better. - The P value of the resin composition of the second low-adhesive agent is used as the material of the material and the aromatic diamine is used for the 322367 15 201139589. The acid anhydride and the aromatic diamine are preferably used at a p value of 1.0 or less. The P value is a value indicating the amount of a polar group contained in the molecule, and is calculated according to the following formula ((1) and (iii)). In particular, the P value of the aromatic diamine is preferably 0.7 or less, more preferably 0.6 or less. The P value of the aromatic tetracarboxylic anhydride = (Α1/Β1) χ1〇〇 (ii) The aromatic diamine P value = (A2/B2)xl〇〇...(iii) [herein 'A Bu A2, B Bu B2 is the meaning of the above sound sample>.) Standing on the above P value, as suitable for use Polyimine resin Examples of the aromatic tetracarboxylic anhydride in the preparation of the precursor include 3,3',4'4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3,4,4,_benzol Ketone tetracarboxylic dianhydride (BTDA), 3,3,4,4,-diphenyl sulfone tetracarboxylic dianhydride (DSDA), pyromellitic dianhydride (PMDA), etc. Among them, particularly desirable acid anhydrides, List 3, 3', 4, 4'-biphenyltetrahydro acid dianhydride (bpda), 3, 3, 4, 4, - dimercapto ketone tetracarboxylic dianhydride (BTDA), etc. These aromatic four The carboxylic acid anhydride may be used in combination of two or more kinds thereof. Further, the above-mentioned P value may be suitably used for the aromatic diamine prepared by the polyimine resin, for example, 2, 2- Double [4-known basic milk base] Bingyuan (BAPP), 2, 2'-diethyl bake-4,4,-diaminobiphenyl (VAB), 2, 2'-dimercapto-4 , 4,-diaminobiphenyl (m-TB), 2, 2'-diethyl-4,4'-diaminobiphenyl, 2, 2,6,6, _tetramethyl-4 , 4'-diaminobiphenyl, 2, 2'-diphenyl-4,4,-diaminobiphenyl, 9,9'-bis(4-aminophenyl)phenanthrene, etc. For the diamine component, 2, 2-bis (4- Benzooxyphenyl)propane (BAPP), 2 2,divinyl-4,4'-monoaminobiphenyl (VAB), 2, 2'-dimethyl-4,4'-diamine Base benzene (m-TB)] 6 322367 201139589, etc. These aromatic diamines can be combined in combination of 2 or more types. In the preparation of the polyimine resin precursor, the diamine oxime used as one of the raw materials is exemplified by the above-described diamine-based oxyhydrogenation represented by the general formula (3). By introducing a oxoxane backbone into a polyimide resin using a diamine oxime, it is possible to impart fluidity at the time of heating and pressing in the adhesive resin composition of the present invention, and it is possible to improve the filling property on the printed circuit wiring. . Specific examples of the diamino sulfoxane represented by the general formula (3) are preferably a diamine oxirane represented by the following formulas (9) to (13), wherein the formula (9) or formula is further The aliphatic diamine oxirane represented by (10) is preferred. These diaminopyridoxane may be used in combination of two or more kinds. In addition, when two or more kinds of diamine oxiranes are combined, 100 parts by weight of the aliphatic diamine oxirane represented by the formula (9) or the formula (10) is used for all of the oxane diamines. It is preferable to mix 90 parts by weight or more. Further, in the formulas (3) and (9) to (13), the mi of the average number of repetitions is in the range of 1 to 20, preferably in the range of 5 to 15. When mi is less than 1, the filling property is lowered as an adhesive, and if it exceeds 20, the adhesion is lowered.

CH3 H3C

I. I H2N—(-H2C-3j(-Si-0-)mi Si—(-CH2~)jNH2 (9) CH3 h3c ch3 h3c

I. I H2N-(-H2C-^-(-Si-0-)^i-Si-(- CH2-)4-NH2 · _ · (10) CH3 H3C ch3 h3c

17 322367 201139589

CH3 HsC H2N—0—H2C~(~Si-0 )mi Si—CH2—0~^^~·ΝΗ2 ·.. (12) CH3 h3c

H2N-{-H2C-)jf-Si-0 Si-¢-CH2~)^NH2 • (13) ό ό The above acid anhydride and diamine may be used alone or in combination of two or more. Further, an acid anhydride or a diamine other than the above may be used in combination. The polyimine resin having the constituent units represented by the general formulas (1) and (2) is obtained by reacting the above aromatic tetracarboxylic anhydride, diamine sulfoxane and aromatic diamine in a solvent to form a precursor resin. It is then manufactured by heating the closed loop. For example, the acid anhydride component and the diamine component are dissolved in an organic solvent in an approximate molar amount, and stirred at a temperature in the range of 0 to 100 ° C for 30 minutes to 24 hours to be polymerized to obtain a polyimide resin. Precursor poly-proline. At the time of the reaction, the reaction component is dissolved so that the resulting precursor is in the range of 5 to 30% by weight in the organic solvent, desirably in the range of 10 to 20% by weight. Examples of the organic solvent used in the polymerization reaction include N,N-didecylguanamine, N,N-dimethylacetamide (DMAC), N-mercapto-2-pyrrolidone, and 2- Butanone, dimercaptosulfoxide, dinonyl sulfate, cyclohexanone, dioxan, tetrahydrofuran, diglyme, triglyme, and the like. These solvents may be used in combination of two or more kinds, and aromatic hydrocarbons such as xylene or toluene may be used in combination. The precursor to be synthesized is usually used as a reaction solvent solution to have a concentration of 18 322 367 201139589, but may be concentrated, diluted or substituted with other organic solvents as needed. Moreover, the precursors generally have excellent solvent solubility and are advantageous in use. The method of imidizing the precursor hydrazine is not particularly limited. For example, in the above solvent, heat treatment for heating at 1 to 24 hours may be employed at a temperature in the range of 80 to 400 °C. When the adhesive resin composition of the present invention is prepared, the compounding ratio of the acid anhydride component and the diamine component of the raw material is not particularly limited as long as the P value can be controlled to 7% or less. For example, the blending of the acid anhydride component and the diamine component The molar ratio is such that the terminal substituent of the polyimide resin is an amine group (that is, the acid anhydride group is blocked with a diamine group), and from the viewpoint of suppressing the polarity of the polyimide resin, the acid anhydride component: The diamine component is preferably from 1. 000 ·· 1. 001 to 1.0:1.2. Further, the polyimine resin having the constituent units represented by the above formulas (1) and (2) is obtained by reacting an aromatic tetracarboxylic anhydride, a diamine sulfoxane and an aromatic diamine. The structure of the amine, the structure of the complete ruthenium is most ideal, and it is also important to suppress the induction of copper diffusion. However, a part of the polyimide resin may also be a proline acid. In this case, the unreacted guanamine sites (-CONH- and -COOH) are regarded as polar groups which induce the diffusion of copper. That is, one proline is calculated as a substituent having four polar groups (two of -CONH- and two of -COOH). In this case, it is preferred to imidize the hydrazine in such a manner that the P value of the composition is 0.7 or less (preferably 0.6 or less). The ruthenium imidization ratio was measured by Fourier transform infrared spectroscopy (FTIR) (commercial product: FTVIR620 manufactured by JASCO Corporation), and the infrared absorption spectrum of the polyimide film was measured by a single reflection ATR method to 19 322 367 near 1015 CHT1. 201139589 The benzene ring absorber was used as a reference and was calculated from the absorbance of the C=0 stretching vibration frequency of the 1780 CHT1 from the quinone imine group. When the adhesive resin composition of the present invention is used for the formation of an adhesive layer of a cover film, in order to exhibit a particularly advantageous effect, for example, the acid anhydride component and the diamine component of the raw material are used in the following combinations of A to C. good. A) Aromatic tetracarboxylic acid: from 3,3'4,4'-biphenyltetracarboxylic dianhydride (6卩0-8) and 3,3'4,4'-diphenyl ketone tetracarboxylic dianhydride (BTDA) Select one or more; B) Diamine-based oxyhydrogenation: a diamine oxirane represented by the above formula (9) or (10) (the weight average molecular weight is preferably in the range of 230 to 1,000) And C) aromatic diamine: 2, 2-bis(4-aminophenoxyphenyl)propane (BAPP). In addition, the blending ratio is set to 75 in the component B from the viewpoint of the solubility of the polyimide resin, the low warpage property of the cover film, and the flexibility. Up to 100% by mole: 25 to 0% by mole, preferably at 80 to 90% by mole: 20 to 10% by mole is preferably set to 80 to 85% by mole · 20 to 15% by mole Ideal. By blending the components A to C in the above ratio, the resulting polyimide resin is excellent in adhesion as a cover film of the adhesive layer. More specifically, the peel strength of the copper wiring layer after the long-term heat resistance test in the air at 150 ° C for 1000 hours may be 0.20 kN / m or more. Such extremely high peel strength is not possible with conventional cover films and is the first implementation in accordance with the present invention. In addition, when the mixing ratio of the component B of the total diamine component is 75 mol 20 322367 201139589 / or more, the polyimide solvent can be provided with excellent solvent solubility, and further, the plasticizer can be prevented from covering. The warpage of the film. The adhesive resin composition of the present invention and the above-mentioned polyamidene resin may contain a plasticizer. However, plasticizers contain a large amount of a polar group of a plasticizer, which promotes the diffusion of copper from the copper wiring. Therefore, it is preferred that the plasticizer is not used as much as possible. Further, as described above, in the adhesive resin composition of the present invention, the molar ratio of the diamine-based calcination of the general formula (3) in the total diamine component in the raw material is set to 75% by mass or more, even if no plasticity is added. The agent can also obtain sufficient softness = to prevent the film from being warped. Therefore, when a plasticizer is to be used, it is preferred to blend in a range which does not impair the effects of the present invention. When the plasticizer is blended in the adhesive resin composition of the present invention, the index p value indicating the amount of the polar group contained in the composition is 〇 7 or less, and preferably 6 or less. At this time, the p value is calculated based on the following formula (iv). Ρ^ = {(ΑΗΑ2+Α3)/(ΒΗΒ2+Β3)}χΐ〇〇...〇ν) [here, Α卜Α2, Β卜Β2 has the same meaning as before, Α3=(polarity in plasticizer) Number of bases χ (molar number of plasticizer) Β 3 = (molecular weight of plasticizer (molar number of plasticizer) The number of polar groups is calculated as described above.] The above enthalpy value is only 0.7 or less. Even if the plasticizer is blended, the effect of the brightener is not impaired. Therefore, the type and amount of the plasticizer to be blended with the adhesive component of the adhesive resin composition of the present invention are as long as the ρ value is & The imine can be used without any limitation. As a plasticizer, for example, a plasticizer such as a phosphate ester, an phthalic acid material, a (four) system, a 322367 21 201139589 fatty acid ester system, etc., for example, in a phosphate ester system. Among the 'may be listed: tridecyl succinate, triethyl sulphate, tributyl acid ester, triethyl 2-ethylhexyl ester, tributoxyethyl phosphate, trioleyl carbonate, triphenyl phosphate Ester, tridecyl phenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, diphenyl phthalate, phosphoric acid (2-ethylhexyl) Further, examples of the polyester system include 1,3-butylene glycol adipate. Further, in the phthalic acid ester system, for example, dimethyl phthalate may be mentioned. Diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, phthalic acid Isodecyl ester, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate, etc. Further, in fatty acid esters, for example Examples thereof include dinonyl adipate, diisobutyl adipate, dibutyl adipate, di-2-ethylhexyl adipate, diisononyl adipate, dibutylene adipate. Ester, di-2-ethylhexyl sebacate, dinonyl sebacate, dibutyl sebacate, di-2-ethylhexanoic acid, and acetyl ricinolate The plasticizer may be used in combination of two or more kinds. The compounding amount in the case of using a plasticizer is, for example, 10 parts by weight or less, preferably 2 to 7 parts by weight, based on 100 parts by weight of the polyimine resin. Following the invention In the resin composition, even when a plasticizer is used, the molar ratio of the diamine oxirane in the total diamine component of the raw material can be set to be more than 75 mol%, and the plasticizer can be blended more than before. Further, in the adhesive resin composition of the present invention, the p value is 〇7 or less, and the polyimine resin described above and the plasticizer 322367 22 201139589 of any component are required. Other resin components such as an epoxy resin, a curing accelerator, a light-binding agent, a filler, a pigment, etc. may be appropriately blended. When such an optional component is blended, the following formula which is modified by the above formula (iv) ( v) Calculate the P value of the entire composition of the adhesive containing all the optional components. P value = {(A1+A2+An)/(B1+B2+Bn)}xl00 (v) [Here, A1, A2, B1, B2 have the same meaning as described above,

An= (number of polar groups in one arbitrary component) x (molar number of arbitrary components) '

Bn = (molecular weight of one arbitrary component) χ (the number of moles of any component),

An and Bn are added to each of the arbitrary components. Further, the number of polar groups in Ren Yincheng is calculated in the same manner as described above]. In the case where the adhesive resin composition of the present invention is blended with an optional component, it is preferable to set the combined amount of the optional components in an amount of 1 to 1 part by weight based on the weight of the polyimine resin (10) by weight. It is better to set the amount of 2 to 2^.垔 知 乂 乂 乂 乂 乂 乂 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 接着 接着 接着 接着 接着 接着 接着 接着 接着 接着 接着 接着 接着 接着 接着 接着 接着 接着 接着 接着 接着 接着An ideal material of the agent can be coated with a film for covering after coating the state of the adhesive liquid of the present invention on one side of the cover layer (4), for example, by a line of 13 〇. The layer is coated with the state of the layer of the adhesive or the solution of the material, for example, after drying at a temperature of 322367 23 201139589 degrees of 80 to 丨8 ,, which is followed by the above-mentioned invention. (10) The film for covering the cover film of the present invention is not limited to the sound, but may be, for example, (IV) imine difficult, poly (tetra) bribe, (iv) amine quinone imine resin (Q) A resin film, a secret (4) resin film, a polyester resin film, etc. In this case, it is preferable to use a polyimine-based resin film having excellent heat resistance ▲. The thickness of the film layer for coating is not particularly limited. Limited, but for example, 5 (four) or more feet below m is preferred. The thickness of the adhesive is not In particular, it is preferable to use a thickness of at least m or less. In addition, since the adhesive resin composition of the present invention is formed into a film shape, it can also be used as, for example, a b-ing sheet of a multilayer FPC. In the case of the base film of (4), the resin composition of the present invention is applied in the form of a solution, for example, after drying at a temperature of 8 to 18 Torr, it may be peeled off. The film may be used as it is. The adhesive film may be used in a layered manner on any of the substrate films. Alternatively, the cover film or the subsequent sheet may be adhered to the adhesive on the adhesive surface. The form of the profile layer is not particularly limited as long as it can be peeled off without damaging the cover film or the form of the sheet, and for example, polyethylene terephthalate (polyethylene terephthalate) or polyethylene can be used. A resin film such as polypropylene, or a film in which such a resin film is laminated on paper, etc. 322367 24 201139589 The circuit board of the present invention is not limited in structure as long as it is equipped with a cover film or a sheet obtained as described above. For example, a preferred embodiment of the circuit board of the present invention includes at least a base material, a wiring layer made of a metal such as copper formed in a predetermined pattern on the base material, and a cover layer covering the wiring layer. The cover film is not particularly limited as the substrate of the circuit board. However, it is FPC Xiao, and it is preferable to use the same material as the above-mentioned cover film. The base material using the polyimide resin is preferable. The circuit board of the present invention is a cover film which is filled with a good recording property and a thermoplasticity by a cover film, and a cover film and a wiring layer are highly dense. Further, by using P The value of the adhesive composition of 〇.7: 乂: forms an adhesive layer, and it is possible to suppress the diffusion of copper from steel, and it is excellent in adhesion even when used in a high-temperature environment. More specifically, after the two-stage, long-term heat resistance test in the atmosphere, the dispersive type x-ray (10) X) is analyzed by the example) 'the amount of copper diffusion to the subsequent layer „ ^ 八,,,°, long-term heat resistance The peeling strength of the film layer for the copper wiring layer after the property test can be maintained at 〇.2 kN/m or more, and the Ar group, the Ri group and the R2 group in the formulas (1) and (2) are selected; the amine/m or higher is extremely high. Separation strength. In addition, the ratio of === money burning is set at 75 Mocher's two-bend bend. And 'read' can prevent the person who covers the film from being able to prevent the circuit board from being able to do it even if it does not match the plasticizer. In this day, #, θ Φ 殿 夕 层 电路 电路 电路 电路 电路 电路 电路 电路 电路 电路 电路 电路 电路 电路 电路 疋 疋 疋 , , , , , , , , , , , , , , , , , 322 322 322 322 322 322 322 322 322 322 322 322 322 322 The production of the circuit board of the present invention is not particularly limited. For example, a metal foil of a metal-clad laminate such as a copper-clad laminate is circuit-processed by chemical etching or the like. After the pattern, a layer of the cover film is laminated on the necessary part of the circuit, for example For example, the pressure-bonding condition is not particularly limited, but the pressure-bonding temperature is 130° C. or higher and 200° C. or lower, and the pressure is 0. IMPa or more and 4 MPa or less. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to these examples. Further, in the following examples, various measurements and evaluations were carried out in accordance with the following methods unless otherwise specified. [Measurement of strength] Next, the adhesive surface of the test piece having a width of 100 mm and a length of 100 mm was placed on a shiny surface of a copper foil (thickness of 35 // m) (excluding rust preventive metal) to 180 After hot-pressing under conditions of °C, 4 MPa, and 60 minutes, a tensile tester (made by Toyo Seiki Co., Ltd., strograph-Ml) was used to stretch the peeling force at a speed of 50 mni/min in the direction of 180° as the strength. In this test, it is judged as "OK" when the intensity is 0. 2kN/m or more, and "good" when it is 0. 35kN/m or more. [Measurement of Weight Average Molecular Weight] The weight average molecular weight was measured by gel permeation chromatography (manufactured by Tohsoh Corporation, HLC-8220GPC). The standard material is polystyrene, and the developing solvent is N,N-dimercaptoacetamide. [Measurement of the amount of diffusion of copper] 26 322367 201139589 - The amount of diffusion of copper is analyzed using an energy dispersive X-ray (EDX) analyzer (manufactured by Horiba, Ltd.). The accelerating voltage was 16 kV, the emission current was 50.0 / A, and the collection time was 6 sec., and the obtained surface concentration was taken as the diffusion amount to the steel of the subsequent layer. The amount of diffusion of copper to the subsequent layer is a value expressed as a percentage of the mass of the copper atom with respect to the mass of the metal atom to be detected. [Evaluation method of warping] The warp is evaluated by the following method. The polyimide polyimide was coated on a Kapton film having a thickness of 25/m to have a thickness of 35/m after drying. In this state, the Kapt〇n film was placed downward. The average height of the four corners of the film was measured, and it was judged as "good" by 5 mm or less, and "bad" when it exceeded 5 mm. The abbreviations used in the present lambda scheme indicate the following compounds. BPDA · 3,3,4,4'_di-p-tetradecanoic acid dianhydride (polar basis of BPDA: 〇, ρ = 〇 · 〇〇) ΒΤΜ . 3, 3, 4, 4 - two clumsy g Dihydrogenated livers of the four enzymes (polar group of BTDA: 1, ρ value = 〇. 56) DSDA. 3,3,4,4 - di-p-styl hard tetradecanoic acid di wild (polar base of DSDA: 2, ρ value = 〇· 93) ΒΑΡΡ : 2, 2-bis(4-amino-p-phenylene)propane (polar group of hydrazine: 2, ρ value = 〇. 53) ΗΑΒ : 4, 4' - (3, 3' _Dihydroxy)diamine-based stupid (ΗΑΒ polar group: 2, ρ value = 〇98) VAB -2,2--diyl _4, 4'-diamine phenyl 322367 27 201139589 (VAB Polar group: 〇, p value = 〇〇〇) DOS: adipic acid di-2-ethylhexanoic acid (polar group of DOS: 4) PSX-A: diamine oxirane represented by the above formula (9) ( However, the average value of mi is in the range of 20, and the weight average molecular weight is 740) Ρ value = 1.77) (14) N-12: dihydrazide represented by the following formula (14) (polarity of N-12) Base: 4 Η2Ν\ Λ λ /νη2 Ν (CH2)i〇Ν/ Η Η Synthesis Example 1 Add 1〇〇249 摩尔 in a 1000ml separation flask, 73.41g PSX-A(〇. 0992 莫Ear), 168g Ν-Methyl-2-t each ketone and 112 g of xylene. Further, 36.46 g of BPDA (0·1239 mol) was added to the separable flask, and the mixture was stirred at room temperature for 2 hours to obtain a polyamic acid solution. The polyamic acid solution was heated to 19 (rc, and stirred under heating for 1 hour to obtain a ruthenium imidized polyimine solution a. At this time, relative to the diamine siloxane component of the whole diamine component The molar percentage is 8 % (m value = 〇 8). Further, the "m value" is the molar ratio of the constituent unit represented by the above general formula (1) contained in the polyamidene resin (hereinafter, The same procedure. Synthetic Examples 2 to 5 The polyimine solution b to e was prepared in the same manner as in the synthesis example except that the raw material composition was as shown in Table 1. 322367 28 201139589 - [Table 1] Synthesis Example酝imine tetracarboxylic anhydride aromatic diamine diamine oxime oxane m value P value solution Hw (mole) (mole) (mole) 1 a 27, 863 BPDA (0.1239) BAPP (0.0249) PSX-A (0.0992) 0.8 0. 18 2 b 37, 331 BTDA (0.0610) BPDA (0.0610) BAPP (0.0244) PSX-A (0.0977) 0.8 0. 38 3 c 36,700 BTDA (0. 120) BAPP (0.0241) PSX-A (0.0964) 0.8 0. 55 4 d 21,947 DSDA (0.1163) BAPP (0.0233) PSX-A (0.0940) 0.8 0. 83 5 e 107, 000 BTDA (0.1246) BAPP (0.0374) PSX-A (0.0872) 0.7 0. 55 Synthesis Example 6 in 1000ml I2.26 g of BAPP (0.0299 mol), 44.20 g of PSX-AC 0.0597 mol, and 15.43 g of N-12 (0.069 mol)' I68 g of N-methyl-2 were added to the flask. _ Pyrrolidone and 112 g of dinonylbenzene. Further, 48.11 g of BTDA (0.1493 mol) was added to the separable flask, and the mixture was stirred at room temperature for 2 hours to obtain a polyamidonic acid solution. The polyamic acid solution was heated to 19 (TC, and stirred under heating for 10 hours to obtain a ruthenium imidized polyimine solution f. At this time, relative to the diamine oxime component of the whole diamine component The % is 40% (m value = 〇. 4). Synthesis Example 7 In a 1 〇〇〇 ml separable flask, 34.29 g of β ΑΡΡ (0. 0835 mol) 35. 47 g of PSX-A (0. 0479 摩尔), ΐ· i8g of ΗΑΒ (0. 0055 莫)' 168g of Ν-曱基-2·- than money 嗣 and 112g of diphenylbenzene. Add 49. 〇6g in the separate flask Ds_·1369 mol), stirred at room temperature 322367 29 201139589 for 2 hours to obtain a polyaminic acid solution. The polyamic acid solution was heated to 190 ° C to heat and stir for 1 hour to obtain a ruthenium imidized polyimine solution g. At this time, the molar % of the diamine oxirane component relative to the total diamine component was 35% (m value = 〇.35). Synthetic Example 8 In a 1000 ml separation flask, 34.26 g of BAPP (0. 〇 835 Mo), 35.48 g of PSX-AC 0. 0479 Mo, and 1. 29 g of VAB (0. 〇〇 55 Mohr) were added. ), 168 g of N-fluorenyl-2-pyrrolidone and 112 g of dinonylbenzene. Further, 49.02 g of DSDA (0.168 mTorr) was added to the separable flask, and the mixture was stirred at room temperature for 2 hours to obtain a polyamic acid solution. The polyamic acid solution was heated to 190 ° C and stirred under heating for 10 hours to obtain a ruthenium imidized polyimine solution h. At this time, the molar % of the diamine oxirane component relative to the total diamine component was 35% (m value = 0.35). Synthesis Example 9 In a 1000 ml separation flask, 9.89 g of BAPP (〇. 〇241 mol), 71.34 g of PSX-A (0.0964 mol), 168 g of N-mercapto-2-pyrrolidone and 112 g were added. Xylene. Further, 35.3 g of BPDA (0.120 ml) was added to the separable flask to disturb the room temperature for 2 hours to obtain a poly-aramidic acid solution. The polyamic acid solution was heated to 190 ° C, and heated and mixed for 1 hour to obtain a ruthenium iodide solution i. At this time, the molar % of the diamine dreaming component relative to the total diamine component was 80% (m value = 0.8). To the obtained polyimine solution, 6 g of DOS (0.014 mol) was added as a plasticizer. Synthesis Example 6 to Synthesis Example 9 are shown in Table 2. 322367 30 201139589 [Table 2_ Synthesis Example Polyiminetetracarboxylic anhydride Aromatic diamine diamine decyl ester compound solution Mw (mole) (mole) (mole) (mole) 0) Value Ρ value 6 f 210,000 BTDA (0.1493) BAPP (0.0299) N-12 (0,0597) PSX - A (0.0597) - 0.4 0. 87 7 g 90, 000 DSDA (0.1369) BAPP (0.0835) HAB CO.0055) PSX- A (0.0479) - 0. 35 0. 73 8 h 88,000 DSDA (0.1368) BAPP (0.0835) VAB (0.0055) PSX-A (0.0478) - 0. 35 0. 71 9 i 36, 700 BPDA (0.120) BAPP ( 0.0241) PSX-A (0.0964) DOS (0.014) 0.8 0. 31 ---1 — [Example 1] The polyimine solution a obtained in Synthesis Example 1 was made on a polyimide film (DuPont M.). The product name KaptonENS, length X width X thickness = 200mmx300mmx25 / / m) is coated on one side, and dried at 8 (TC for 15 minutes to form a cover film 1 having an adhesive layer thickness of 35 #m. The surface was placed on a copper foil from which the rust-preventive metal layer was removed, and pressurized under conditions of 18 〇〇c, pressure of 4 MPa, and 60 minutes, and Sample 1 was evaluated. The adhesive strength of the cover film and the copper foil after the adhesive layer was hardened was 0. 67kN/m. Next will evaluate sample 1 The heat treatment was carried out in an oven at 15 (rc for 1 hour). The adhesion strength between the (four) and the cover film after the treatment was measured to be 54 kN/m. The characteristic values of the measurement film are shown in Table 3. [Examples] 2] The film 2 was obtained except that the polyfluorene polyimide solution b in Example 1 was replaced, and the sample 2 was evaluated. The imine solution a was obtained in the same manner as in Example 1 except for the synthesis example 2. The adhesive strength of the coating layer after hardening of the layer was 527367 31 201139589. The copper foil had a subsequent strength of 0.57 kN/m. Next, the evaluation sample 2 was heat-treated at 150 ° C for 1000 hours in an oven. The treated copper foil was measured. The bonding strength of the cover film was 0.38 kN/m. The characteristic values of the measurement film are shown in Table 3. [Example 3] The polymerization obtained in the synthesis example 3 except the polyimine solution a in Example 1 was obtained. The film of the cover film and the copper foil after the adhesion of the adhesive layer was 0. 76 kN/m. The film was obtained by the same procedure as in Example 1. Next, the evaluation sample 3 was heat-treated at 150 ° C for 1,000 hours in an oven. The measured strength of the copper foil and the cover film after the treatment was 0.42 kN/m. The characteristic values of the measurement film are shown in Table 3. [Example 4] The cover film 4 was obtained in the same manner as in Example 1 except that the polyimine solution a in Example 1 was replaced with the polyimine solution i obtained in Synthesis Example 9. Sample 4. The adhesive strength of the cover film after hardening of the underlayer and the copper foil was 0.70 kN/m. Next, the evaluation sample 4 was heat-treated at 150 ° C for 1,000 hours in an oven. The subsequent strength of the treated copper foil and the cover film was determined to be 0.35 kN/ni. The characteristic values of the measurement film are shown in Table 3. [Comparative Example 1] A cover film was obtained in the same manner as in Example 1 except that the polyimine solution a in Example 1 was replaced with the polyimine solution d obtained in Synthesis Example 4, and an evaluation sample was obtained. . The characteristic values of the measurement film are shown in Table 4. 32 322367 201139589 Comparative Examples 2 to 5 Except that the polyimine dissolved in Tables 1 and 4 was used, the same operations as in Example g were carried out. g, h The characteristic values of the measured enthalpy are shown in Table 4. It is estimated that the sample is evaluated. In Table 4, the following strength 1 indicates the adhesion strength of the film after curing of the adhesive layer, and then the strength 2 indicates that it is in the atmosphere = C. (4) after the heat treatment of the face hour and the cover 臈 [Table 3]

[Table 4] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Polyaniline solution defgh Next strength l (kN/m) 0. 42 0. 70 0. 45 0. 18 0. 65 Next strength 2(kN/m) 0. 17 0. 20 0. 00 0. 00 0. 13 Diffusion amount of copper (%) 3. 2 Unmeasured, unmeasured, unmeasured, unmeasured, defective, poor, defective, defective Table 4 shows that, as an adhesive resin composition, in Examples 1 to 4 in which the polypyridamine solutions a to c, i having a P value of 0.6 or less, 33 322367 201139589 = hour after the heat treatment of copper Also, the result is low, and in the embodiment, the decrease in the strength of the strong t is less than the strong second of 〇. Moreover, the thickness of the cover film is also suppressed. Further, since the pro-imine solution i having a P value of 〇·7 or less is used, the strength is finely bonded. On the other hand, a film of the strength after the heat treatment was used in Comparative Examples 3 to 5 in which p:= poly-imine was reduced by d, f to h. Also, the use of m values is not up to:

Comparative Example 2 + of the brewing imine solution e, film of the (four) code foot of the cover film. The above is a detailed description of the embodiments of the present invention, but the present invention is not limited to the above embodiments. Many changes may be made by those skilled in the art without departing from the scope of the invention, which is also included within the scope of the invention. For example, in the above-described embodiment, the use of the adhesive resin composition of the present invention is a cover film or a sheet of a circuit board such as Fpc, but the adhesive resin composition may be used in the above-mentioned outer layer. For example, the formation of a resin is followed by, for example, tape automated bonding (TAB), chip size package (CSP), and the like. [Simple description of the diagram] None. [Main component symbol description] None. 34 322367

Claims (1)

201139589 VII. Patent application scope: 〇〇, νλαλ ΝγΑ "丫N-Rl' Ο ο I ^ The adhesive resin composition is a polyimine containing the constituent units represented by the following general formulas (1) and (2): (1) m νΑ ο 〇ο ΑΓΥΝ· ο (2: η [wherein, the Ar table is not a tetravalent aromatic group derived from an aromatic tetracarboxylic anhydride.] Rl is a divalent diamine silk oxygen produced by the second wire. a fluorenyl group, R2 is a divalent aromatic diamine group derived from an aromatic diamine, and a group η represents a molar ratio of each constituent unit (4), in the range of 4^ to ^, and η is in the range of 〇 to 〇. Further, the ruthenium value of the present resin composition is 0.7 or less, and the enthalpy value is an index indicating the amount of the polar group contained in the composition, and according to the following formula (1), the nose Ρ value = {(Α1+Α2) )/(Β1+Β2)}χ100 (1) [here, the number of polar groups in the AWAr group) x (the number of moles of the Ar group) A2 = (the number of polar groups in the R2 group) x (R2) The number of moles of the base) Bl = (molecular weight of the Ar group) x (the number of moles of the Ar group) B2 = (the molecular weight of the RZ group) X (the number of moles of the R2 group) The number of the aforementioned polar groups is: -x (x indicates tooth Atom), -OH, _SH, _〇...a s_, _s〇_, __, 322367 1 201139589 ~C0-, -CN-, _P=0, -P〇- respectively as one, -S〇2- , -C0NH- respectively as 2, -SO3H- as 3, and calculate] 2. The adhesive resin composition as described in claim 1, wherein the synthesis of the aforementioned polyimine resin is used The aromatic tetracarboxylic anhydride and the aromatic diamine having a p value of 1.0 or less are used as a raw material, and the p value is an index indicating the amount of a polar group contained in the molecule, and is calculated based on the following formulas (ii) and (iii). , P value of aromatic tetracarboxylic anhydride = (A1/B1)xl〇〇...(ϋ) P value of aromatic diamine = (A2/B2)x100 ... (iii) [here, A1, A2 B1 and B2 have the same meanings as described above. 3. The adhesive resin composition according to the second aspect of the invention, wherein the P value of the 'aromatic diamine is 〇. 7 or less. The adhesive resin composition according to Item 2 or 3, wherein the polyimine is synthesized by using a diamine siloxane as shown in the following general formula, Rs R7 H2N-R3 —f S丨i一.^^:丨R"NH2 ...(3) Re R8 [wherein R3 and R4 respectively represent a divalent organic group which may also contain an oxygen atom, and Rs to 匕 respectively represent a carbon number of 丨6 The hydrocarbyl group has an average repeat number of mi of 1 to 20]. 5. The adhesive resin composition according to claim 4, wherein the molar ratio of the diamine 矽2 322367 201139589 oxane of the above general formula (3) in the total diamine component of the raw material is 80% or more. 6. The adhesive resin composition according to any one of claims 1 to 5, further comprising a plasticizer, wherein the index P value indicating the amount of the polar group contained in the composition is 0.7 or less, and the p value is as follows. Equation (iv) calculates, P^ = {(Al+A2+A3)/(Bl+B2+B3)}xl〇〇...(iv) [here, A1, A2, B1, B2 are the same as described above The meaning, A3 = (number of polar groups in the plasticizer) χ (molar number of plasticizer) Β 3 = (molecular weight of plasticizer) χ (molar number of plasticizer), the number of polar groups is The same calculations as described above]. 7. The adhesive resin composition as described in the above paragraphs to 6 of the patent application is used as a cover for protecting the wiring portion of the circuit board. A cover film formed by laminating an adhesive layer and a film for covering, wherein the adhesive layer is formed using the adhesive resin composition described in the items i to 6 of the patent application. A circuit board of the invention includes a substrate, a wiring layer formed on the substrate, and a cover film of claim 8 covering the wiring layer. 2kN The peeling strength of the wiring layer and the coating film is 0. 2kN, the peeling strength of the wiring layer and the coating film is 0. 2kN /n! Above. 322367 3 201139589 IV. Designated representative map: There is no schema in this case. (1) The representative representative of the case is: ( ). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: R5 R7 II H2N - R3 - (-Si-Ο-ή--S1-R4- NH2 ---(3) I mi I R6 R8 3 322367