TW200819501A - Polyimide-based resin composition, method of manufacturing thereof and metal laminate - Google Patents

Abstract

The present invention relates to a polyimide-based resin composition having an excellent heat resistance property enabling a thermocompression bonding process to be performed at the low temperature, having a high desmearing property (desmearing at a fast speed), and having an excellent easy processing property including the control of the pollution of the processing environment. The polyimide-based resin composition including polyimide and imide oligomer represented by the formula (2) is provided. The polyimide includes repeating units represented by the formula (1-1) and the formula (1-2).

Description

200819501 256Ui)plt IX. Description of the invention: This application claims priority based on the application No. JP2006-244946 (Japanese Patent No. 2 〇〇 6 244 946) filed in September 2006. The contents described in the manual and the drawings are all in support of this case. [Technical field to which the invention pertains]

The present invention relates to a polyamic acid imide resin composition, a method for producing the same, and a gold comprising a resin layer composed of the resin composition. [Prior Art] Characteristics 'Electrical materials used in aircraft structural materials and cable coating It is well-suited as a heat-resistant adhesive for use in the electronic field represented by the printed circuit board and semi-conductive and clothing.浐: 而 and: ϊΐ using a poly-imine-based adhesive as a resin layer of gold imine metal laminate; (2) solder in this polyacid piece of enamel and electronic parts, or remove the so-called spare love tablets The case of winter pieces. From the environmental point of view in recent years, the use of error-free solder has been gradually used in the crystal, so it is necessary to: ~ end, different '" solder heat resistance (10) derheat (four) st_)". In the so-called hard-flexible and flexible multilayer substrate, it has been known in the past (4) that it has a higher temperature resistance. Insufficient, it is desirable that the film is made of a bismuth-based imide-based adhesive as a fine layer of a resin layer, and a film-joined bonded body (hereinafter referred to as "C-mounting wire bonding" using an internal wire bonding machine and a moon bonding 5 200819501

ZDOUDpiI

Au-Au bonding or Au_Sn bonding is performed. Since Au_Au bonding or Au__ requires a south temperature condition of 300 C or more, it is desirable to use a substrate excellent in solder heat resistance even when used in c〇f.吧,工,士 In the recent years, the polyamine-based heat-resistant adhesive, from the plus

> 'W 4 inch! The raw aspect δ, in addition to the heat resistance characteristics, is also gradually required ίίΓ: Right in the past using a resin composition containing a specific poly-acid: ϊ = and =. In the case of the above temperature, the characteristics are not observed from the low temperature and the characteristics are not sufficient. The word ί 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺The resin composition (for example, refer to the patent literature) belongs to the case where the use of a polyimide-based adhesive as a resin layer for the production of gold, and the use of laser processing to perform through-hole-type alkaline dissolution in the through-hole The formation of the treatment of "when the ww bridge material is removed by the laser plus the entire side" (also known as "de-slag treatment"). From the moon layer (also known as the glue to remove the surface of the fast surface (to _ speed ·, Hao ^,, the solubility of the alkaline solution is higher in the relaxation of the imine system: the: period: can make J still low temperature adhesion After the polyimine is followed by 'two two and two easy to slow. The slag speed part of the agent, ί:: two charge f low temperature adhesive polyimine series followed by reports from the double Malay Amine compound and poly-branched acid formed by 200819501

ZDOU^piI resin composition (refer to Patent Document 5). However, when the resin composition containing bismaleimide is used for the resin layer of the metal laminate, a volatile substance (bismaleimide) may be generated due to the conditions, and sometimes it may be produced. The problem. Also, when coating or laminating the resin composition, there is a volatile matter when it affects the production equipment. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei 2〇〇4_2〇9% No. 2 [Invention] The object of the present invention is to maintain the second gelatinous composition of the composition of the polyurethane-based tree Go to the plastic money). Further, the object of the present invention is to suppress the generation of volatile substances during processing, and to form a polyimine-based resin composition. The metal laminate of the substrate or the like is printed by using the resin composition of the present invention. Applicable crops. The first! The present invention relates to a polyimine-based tree composition composition shown below (!H species = a lion-like composition, which contains the following general formula of the imiline tree, and the following general formula (2) :^Heavy amine:=7 200819501

JOLDpiT

A Α2 ΟΛ\ηο ΟΛ^ΥΟ ΟΛ ϊο οαβϊο ? JN) -2) [In the formula (Η) and (1-2), Afen Δ γ or (a2), both of them can be the same; β aj or (b2), which can be the same or different from each other]] 2 is not the following formula (7) Xr°O^0iy ··-

〇〇 Δ Λ Λ Α3~Ν Β3 Ν- ϊ If 〇〇 (a2) 〇 (b2) (bl)

(2) [In the formula (2), Α3 is the following formula (cl is an integer of 1 to 5 in the following formula (dl) to (d4)]

One of ~(c4), one of b3, z is the following formula (el) or (e2)M (c2) (cl)

(c3) (c4) [In the formulas (cl) to (c4), χ7~12 are selected to contain single bonds 〇~, -S-, one CO-, -COO-, ~cr, ~C(CFS) 2 S02 NHCO- group, which can be mutually correlated 8 200819501

230UDpiI

Can also be different]

Ve4 Υ1〇{|- (dl)

丫 7-·

• (d4) (d2) Υ9 Υΐ1 [In the formulas (dl) to (d4), Υ7~12 are selected to contain a single bond, 〇S---CO COO---c (ch3) 2___ c(cf3) 2 so2 NHC〇- group, which can be the same or different) R1 (el)

(e2) [In the formula (el) or (e2), Rh is selected from the group consisting of a hydrogen atom, a halogen atom, and an alkyl group having 1 to 3 carbon atoms, which may be the same as each other or different from each other. a 0-, an S-, a CH2 co- or a coo-] c (CH3) 2-

[2] The polyimine-based resin composition according to [1], wherein one of the person of the above formula (1-1) and one of the formula (1-2) of the formula (1-2) is (al), One party is (a2). [3] The polyimine-based resin composition of [2] or [2], wherein 1 of the above formula (2) is 1. [4] The polyimine-based resin composition according to any one of [1] to [3] wherein, in the above-mentioned by weight of the above-mentioned polyimine resin,

The quinone imine oligomer represented by the formula (2) contains 5 parts by weight or more and 1 part or less. S [5] The polyimine oxime resin composition according to [1], wherein the glass transition temperature is a range of just W and below. The composition of the composition of B3 is selected from the following formula (du r ', ^^ (D) or (C6), Γ) 0C · - 54乂1 is an integer of 1 to 5. The prince of dl°) is (e3: "t^r〇~O~〇-01- · · (〇5) (d7)

(d9) ϋ [The definitions of R3 and R4 are the same as those of the above formula (e2)] [7] A mixture containing the repeating unit represented by the following formula (n) and the following formula (3-2) The repeating unit of polyamic acid, the quinone imine oligomer represented by the formula (2), and the solvent required at the time. (3-1) μ 〇 Ο Μ ' -Af Ν-4

ΗΟπί ir0H 〇〇 10 200819501 ZDOU^pil

• * * (3-2) ^ [ff) (3Β;^ί } ^ 5 (al )Ϊ ^,= 'can also be different, and B2 is the aforementioned gas ") ΐ : 1 ' can be identical to each other, Can also be different] Α3-ΝΛΒ, Ν Π γ γ 〇

〇χΥ I 〇,,, [in the formula (2) towel '^ is one of the above formulas (cl) to (c4), Β, is one of the other formulas (dl) to (d4), 7 Yanyi , +, 4, 2 are in the elliptical formula (el) or (e2), and 1 is an integer of 1 to 5] [(7) A method for producing a cured polyimide resin, which comprises heating as in [7] The mixture is used to initiate the amination reaction. And [9]-face, which is a cured product of the polyamidene-based resin composition according to any one of (1) to (4). (10) A metal laminate comprising a metal layer and a resin layer, and at least one layer of the resin layer is a cured product of a polyamic acid imide resin composition according to any one of [n to [6] Composition. [11] A metal laminate comprising a polyimide film, a polyimide layer formed on one or both sides of a rhodium imine film, and a layer of the polyimide layer a metal layer of one or both of the layers; a polyimine layer-based resin layer which is in contact with the metal layer, which is cured by a poly-blue imine resin composition according to any one of [1] to [6] The composition of things. l 12 connector picture

200819501 -^OUDpn The π,] to the single-sided or double-sided of the resin film, [there are 6 trees „ layered in the hardened material of the pro-amine resin composition, which constitutes the money of the invention. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Then, it is not necessary to use f = processing temperature 'minus _ to remain in the box layer and (iv) imine interface 2: the metal layer and the resin layer are higher than the metal layer - the metal layer can be suitable for use As a flexible printed circuit board or the like: = the metal laminated body and the succeeding sheet of the metal laminated body precursor, and the sheet (the sheet in the state without the metal layer) are excellent in solder heat resistance, so the LSI having strict f-preparation conditions is required. In the wafer or part mounting process, and in the spare parts manufacturing process, expansion is also difficult. [Embodiment] 1. Polyimine-based resin composition The polyimine resin composition described herein is characterized by: Contains poly-Asian tree sap and oligomers of imines (eg 〇lig Mer) The polyimine resin contained in the polyimine resin composition may also be a repeating unit and a formula represented by the following formula (μ). a repeating unit shown; or a precursor of a repeating unit represented by the following formula (Μ) and a repeating unit represented by the formula (1_2) by imidization (also 12 200819501 256ϋ5ριί is a polyfluorene) Poly amic acid 〇ο (1-1) (1-2) Δ ΛΑ

1 W 〇〇〇〇 Λ Λ Λ Α Α Ν Ν Ν Ν Ν ϊ ( ( Ν Ν ( ( 1-1 1-1 1-1 1-1 Α Α 及 及 及 及 及 及 及 及 及 及 么 么 么 么 么 么 么 么 么 么 么 么 么 么 么 f f f f f It has a structure of two adjacent sub-bonds (tdphenyleneether), and the following formula (al) (al) W°W°Y^ ______ 〜, "$U2) indicates. (a2) A] & A2 may be identical to each other or different from each other. Preferably, the sum is - (al) and the other is (a2). When the field ^ is (4), sometimes the desmear speed will be slower. On the other hand, when ΑιΑΑ2 is (10), the peel strength and the low-temperature adhesion may be lowered. When the combination of ^ and ~ is (3)) disc c;, the balance between the de-speed and the low-temperature adhesion (glass transition temperature) can be obtained, so the ratio of (al) to (a2) contained in the polyimine is higher. Good for 8: 2~5: 5, better for 7: 3. Further, BAB2 of the formula (1) is represented by the following formula (Μ) or (b2). It is preferable that the degreasing speed of the resin composition can be improved when the combination of (a) or both of (or) and (b) is improved, but another aspect, When the ratio of b2) is too high, sometimes it is in the humidifying ring; the solder heat resistance will deteriorate. II η

lJ Uk ··- X)r§XX ··-) The polyimine tree 13 contained in the polyamidene resin composition of the present invention has a repeating unit lipid as shown in 200819501 256ϋ5ριί, although it contains the above formula (1) -1) and (1-2) but may also contain other repeating units. The molecular weight of the polyimine resin contained in the polyimide composition is not particularly limited, and the domain can be decomposed (diami=f tetracarboxylic acid dianhydride). The molecular weight and its molar ratio are adjusted.制造 Manufacture of polyimide resin

The polyimine resin contained in the composition of the polyamidene resin is preferably produced from a raw material of tetradecanoic dianhydride and diamine. Among the raw materials of the polyimine resin, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) containing tetracarboxylic dianhydride is preferred. Or bis(3,4-dicarboxyphenyl) sulfonic dianhydride (DSDA) 〇 In addition, one of the raw materials of the polyimide resin may also be included. Or two or more other tetracarboxylic dianhydrides. When these copolymerizations are carried out, the performance and modification of the properties of the polyimide resin can be carried out without damaging the effects of the present invention. In the case of other tetracarboxylic dianhydrides, it includes: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether Dianhydride, bis(3,4-dicarboxyphenyl) sulfide dianhydride, bis(3,4-dicarboxyphenyl)methanthine, 2,2-bis(3,4-dicarboxyphenyl) Propane dianhydride, 2,2_bis(3,4-diweilcyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis(3,4-di Carboxyphenoxy) succinic anhydride, 1,4_bis(3,4-dicarboxyphenoxy)phthalic anhydride, 14 200819501 256ϋί) ριί 1,4-bis(3,4-dicarboxyphenoxy) Biphenyl dianhydride, 2,2-bis[(3,4-dicarboxyphenoxy) phenyl] propane dianhydride, and the like. Further, in the case of other tetracarboxylic dianhydrides, ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclodecane tetracarboxylic dianhydride, 1,1-bis (2,3- Dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, U-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1, 2·bis(3,4-dicarboxyphenyl)ethane two-needle, 1,2,5,6-natetradecanoic acid two-needle, 3,4,9,10-flower tetracarboxylic dianhydride, 2, 3,6,7-decanetetracarboxylic dianhydride, 1,2,7,8-naphthalenetetracarboxylic dianhydride, and the like. These tetracarboxylic dianhydrides can also be used individually or in combination of 2 or more types. Further, the other tetracarboxylic dianhydride may be a part of the hydrogen atom on the aromatic ring of the above-exemplified tetracarboxylic dianhydride or a total of four tetrahydro acid dianhydrides, which may be substituted with a fluorine group or a trifluoromethyl group. Among the raw materials of the polyimine resin, 1,3-bis(3-aminophenoxy)benzene (hydrazine) or 1,3-bis(4-aminophenoxy)benzene containing diamine is preferred. (APB-R), better to contain any kind. The raw material of the polyimide resin may also contain other diamines. Other diamines may be either aromatic diamines or aliphatic diamines. In the aromatic diamine, it contains m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 4, diamino Diphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3 diaminodiphenyl hydrazine, 3,4f•diaminodiphenyl hydrazine, 4,4′-diaminodiphenyl hydrazine, 3,3′-diaminodibenzophenone, 3,3f-diaminodiphenyl decane, 3,4′ _ Aminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-dual ( 3- 15 200819501 256ϋ5ρΐί ^ ^33 H ,,6 垸 垸, 2,2·bis(4-aminophenyl)-u, thixo, fluoropropane, diaminodiphenyl sulfoxide, 3 dimethylamino Stupid Azolla, 4'-diamino-secondary stony wind, (3) bis(3-aminophenyl) stupid, 1,3: yet (4-northylphenyl)benzene, bis (3_aminophenyl)benzene, -Bis(I)_~bis(3.aminophenoxy) stupid, 1,4-bis(4-aminophenoxypurine + Ϊ '4 bis(3_aminophenyl sulfide)*, U_double (4_ Aminophenylsulfide^bis(4)aminophenylsulfur (6) stupid, bis(3.amino) Hard)

Ben,, - (4-milylbenzene mill) benzene, double (Guang double corpse: ammonia fresh) benzene, U, (4_ amino bamboo benzene, M_ double, heart amino section) benzene, 1,3· Bis(3.amino-4-phenoxybenzoquinone) stupid, 3 3_bis(3-aminophenyloxy)biphenyl, anthracene bis(4•aminophenoxy) phenyl, y again (3-amino Phenoxy)biphenyl, 4,4_bis(4-aminophenoxy) linked ^ double! :3·(3—Aminophenoxy)phenyl] succinyl, bis[3-(4-aminophenyl) benzyl]-, bis[4-(3-aminophenoxy)phenyl]ether, double (4-cyclophenoxy)phenyl]-, bis[3·(3-aminophenoxy), yl] ketone, bis[3-(4-aminophenoxy)phenyl]one, bis[ 4·(3_Aminophenoxy)phenyl]one, bis['(4-aminophenoxy)phenyl]one, bis[3-(3-aminophenoxy)phenyl] sulfide, double [3_ (4-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl] sulfide, Bis[3-(3-aminophenoxy)phenyl]sulfone, bis[3-(4-aminophenoxy)phenyl]sulfone oxime bis[4-(3-aminophenoxy)phenyl]indole, double [4-(4-Aminophenoxy) benzyl] zephyr, bis[3-(3-aminophenoxy)phenyl]methyl ketone, bis[3_(4-gas basic oxy) benzyl] , bis['(3-aminophenoxy) 16 200819501 256U^pit Γ phenyl]methane, bis[4-(4-aminophenoxy)phenyl]methane, 2,2_bis(3-aminobenzene Oxy)phenyl]propane 2,2-bis[3_(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[本( 4-aminophenoxy)phenyl]propanol, 2,2-bis[3_(3-aminophenoxy)phenyl]yi^^hexafluoropropane^(bis)·(cardoaminophenoxy)benzene Base]_1,;[,1,3,3,3_hexafluoropropane, 2,2_bis[4_(3-aminophenoxy)phenyl]_i,ij,3,3,3-hexafluoropropyl House, 2,2_bis[4_('aminophenoxy)phenyl], 丄3,3,3_hexafluoropropane, etc. These aromatic diamines may also be used one kind or in combination of several kinds. The raw material of the polyimide resin may also contain an aliphatic diamine. Aliphatic diamines are used for performance improvement and upgrading. In the case of an aliphatic diamine, it contains 1,3-bis(3-aminopropyl)tetramethyldioxane, hydrazine, and 3-bis(4-aminobutyl)tetramethyl oxalate. α,ω bis(3-aminopropyl)polydimethyl bismuth oxide, α,ω-bis(3.aminobutyl)polydimethyldiwei, bis(aminomethyl)ether, 1 , 2-bis(aminooxy)ethane, bis[(2-aminodecyloxy)$yl]ether, 1,2-bis[(2-aminodecyloxy)ethoxy]ethane, double & Aminoethyl)ether, bis(2.aminoethoxy)ethene, bis[2-(2-aminoethyl)ethyl]ether, bis[2-(2-aminoethoxy)B Ethyl bromide, double 3 _ propyl) ether, ethylene glycol bis (domain propyl) _, diethylene glycol bis (3, propyl) _, triethylene glycol bis (3 propyl) ether , Ethylenediamine, ^ ^ ^ i56- Γ κ), ": Feigen, Μ, diamino octyl, W diammonium, U-ring, 1,3-diaminocyclohexane , M-二17 200819501 25605pif Aminocyclohexane, 1,2-di (2^ 7 ^ , 〇苴, Yangkou ^ i, 厶虱ethyl)% hexane, u_二(2_

= 衣冬二(L-aminoethyl)cyclohexane, bis(4-aminomethine P-based ^^6, (aminomethyl)bicyclo[cut], two = 一1% 2,2,1 ～Heptane, etc. These diamines may also be used singly or in combination of several kinds. The bismuth imide resin contained in the 2-amine resin composition is more than the usual shrinkage. The polymerization polymer can be controlled by adjusting the molar ratio of the monomer component as early as possible. In other words, the polyimide material is a tetracarboxylic acid dianhydride which is a non-monoamine, more preferably contains 95 mol of tetracarboxylic dianhydride, and particularly preferably contains 〇95 mol 〇 〇 995 The tetracarboxylic dianhydride of Mo, preferably a carboxylic acid dianhydride containing 〇97 mol to 〇995. The lack of four... The raw material of the polyimine resin (the monomer containing diamine and tetracarboxylic dianhydride) preferably turns into poly-proline (polyimine precursor), and then becomes a poly amine. In order to make the monomer raw material into polyamic acid, it is only necessary to add the monomer raw material and heat it.溶剂 The solvent to which the monomer raw material of the polyimide resin is added is not particularly limited, but is preferably an aprotic polar solvent (&?1*〇1) 〇1虹80^如〇, ^ is an aprotic 醯Amine solvent. Specifically, it can be exemplified by the team of dimethyl thiophene, N,N-methylethyl decylamine, n,N-diethylethylamine, n,n-dimethyl"methyl acetamide , N-dimethyl-2-pyrrolidone, iota, 3-dimethyl-2-tomoxyl, etc. I~ In addition, in the solvent of the monomer raw material of the polyimine resin, 18 200819501

Z30U3piI can be further used to provide a solvent and a solvent as shown below. In the organic solvent that can coexist, chlorine, stupid: a, f, o-xylene, m-xylene, p-xylene, o-bromo, stupid, p-toluene, o-bromotoluene, m-bromotoluene, above species Make ^, fill benzene, etc. These organic solvents can be used alone or in combination with 2 paints. The poly-araminic acid produced by the polyamine precursor is used as a clear heart, and more: the logarithmic viscosity of the plume is secret, preferably 〇.2 dl々~2.0 醯iamine before]·3(1)々~1...dl /g ' is preferably Q.4 dl/g to 0.9 dl/g. The logarithmic viscosity of the poly precursor is a solution obtained by dissolving the viscous yam at 35 °C in the concentration of Q'5dl/g in the solution of -dimethylacetamide. When the logarithmic viscosity of the substance is set within the above range, the metal squeezing and squeezing hardened material becomes firmer, and it is easy to form a film and a ruthenium, and the coating system is easy to maintain at the time of film and metal laminated body production. Uniform film thickness is quite ideal. The yttrium imide oligomer contained in the imine-based oligomer composition has a structure of J1" in the formula 1. 1 in the formula (2) is 1 to 5. The result of the formula (2) is that the effect of improving the effect of the quinone imine oligomer as a plasticizer can be improved. The progress of the two-component bismuth imide resin composition is low temperature followed by 〇ΖΛ\Ν' Ο Xο X If 〇〇〇jf A3i〇Z Υ 〇 (2) 弋 (2) Α 3 has the following formula (cl) ~ ( 19 200819501 joiopir ο f聋 shown in one of c4). Further, the filament in the formula (7) preferably has a structure as shown by the following formula (c5) or (c6). In the formula (1)) ~ ('), (: 6) self-contained single bond, a 0 ~) X7 ~ 12 system

S co , a COO —, — c can be the same or the same. x 1 . — group of NHC0—, π-like from/different 7~12 is bonded to the carbon constituting the stupid ring, and A3 in the formula (2) has the formula (峨)... CH, • C(CF3)2 - so (cl) -x9--

X 10 JT-Xirf -χ12- (c4) -Q-o-0-0-0- ...(c£ (c6) O~°O-〇-〇m〇- ·

• (c7) b3 in the formula (2) has the structure 3 shown by one of the following formulas (~(5)0). ;: with (c8) structure. In addition, in the formula (2), n h is not; the force and cost are equal to the force - the choice is 3. :Under W series chooses self-contained single key...〇...—s — C (10))Π (called r, —so “,————————————————————————————————————————————————————————————————————————————————— 200819501 2^6 UDpir % of one of the anti-atoms of the stone. Also ~ is -coo or -NHC0 The direction of the bond is in any direction. U ...(dl) Y^v7-rr

• (d3) one (d2) (d4) 11

»〇Ί〇ν〇^χχ .··_ h3c ch3 _Yi2~CC ·.· )〇"c »°1〇:

(d9) (d6) (d8) The following formula (ei) or (8) represents the following two groups of hydrogen N-C(CH3)2 co- or -coo-. & is -c(8), and the direction of the bond can be in any direction. (el)

R3, (e2) (e3) R4, ^\ You * The oligomerization of quinone imine contained in the poly (tetra) tree surface of the present invention ‘ preferably has a weight average molecular weight of 1000 or more and 5 Å or less (also 21 200819501)

2^t) U3plI is called Mw). The weight of the quinone imine oligomer is determined by the chromatographic method (determination of the strip thousand =, the gel can be used to infiltrate the four gas 哕 ,, 4, # · 彳 " · cattle for private measurement for · RI, extended catalyst : Four a funan, machine speed. iml / mm, 桎 temperature · 醯 imine oligomer weight flat eight less heating resin composition evaporation] range, can reduce fruit, equivalent _ H * will reduce plasticization The effect is ~, another 攸 攸 墓 墓 墓 - - - - - - - - - - - - - - - - - - - - - - - 丁 丁 丁 丁 丁 丁 丁 丁 丁 丁 丁 丁 , 丁 丁 丁 , , , , , 3500 or less 'preferably 1500 yttrium ylide oligomers can be used in the lipid composition to contain the sulfhydryl amine and the second private spider/coating. For example, it can be used to contain tetradecanoic dianhydride. The second anti-reservative and the dianhydride; = and the solvent to be added if necessary, starting from the imine anhydride: = ί: = each component contained in the raw material (four neodimer (described later). Example 3 of the four acid dianhydrides contained in the raw material of the acid imine low-alcohol, the raw material of the imine oligomer, 3,4 41 tetraisoxic acid, 3,3', 4,4L biphenyl Acid dianhydride, i anhydride: 雔 - four ships Di-anhydride, bis(3,4_two-phenyl) phenyl)i dianhydride diterpene benzene phantom two needles, double (3,4-two county ^ ^ again (3,4·1 decyl benzene) Base) bismuth dianhydride, 2,2_bis]"-di-ylphenyl) dianhydride, 2,2_bis (3,4_two phenyl) H difluoropropanthrene 3,4_二县phenoxy) •, (3,4·carboxyloxy)phthalic anhydride, 1,4_bis (3,4- 22 200819501 ζ^ου^ριτ dicarboxyphenoxy Biphenyl dianhydride, 2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, etc. The tetracarboxylic dianhydride contained in the raw material of the quinone imine oligomer is 1 Or two or more. Examples of the diamine contained in the raw material of the quinone imine oligomer include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 3J-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3f-diaminodiphenyl sulfide bond, 3, cardio diaminodiphenyl sulfide bond, 4,4f-diamino group Phenyl sulfide, 3,3f-diaminodibenz, 3,4'-diaminodibenzamine, 4,4'-diaminodicarbite, ^3,3f-diaminodibenzophenone, 3,3'-diaminodiphenyl decane, 3,4'-diaminodiphenyl Decane, 4, aryldiaminodiphenyl decane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-ammonia Phenyl M, l, l, 3, 3, 3-hexafluoro, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3_hexafluoropropene, 3 , 3'-diaminodiphenylarylene, 3,4'-diaminodiphenylarylene, 4,4'-diaminodiphenylarylene, 1,3_bis(3-aminophenyl)benzene, 1 , 3-bis(4-aminophenyl)benzene, M-bis(3-aminophenyl)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(3-aminophenoxy) Benzene, 1,3-bis('aminophenoxy)benzene, 1,4-bis(3-ammonia, phenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1 , 3-bis(3_aminophenylsulfanium)benzene, 1,3-bis(4-phenylphenylsulfonate)benzene, 1,4-bis(4-phenylphenyl sulfide)benzene, 1,3 - bis(3-aminophenylsulfone)benzene, 1,3-bis(4-aminophenylhydrazine)benzene, 1,4-bis(4-aminophenylsulfone)benzene, 1,3-bis(3-aminobenzyl) Benzene, 1,3-bis(4-aminobenzyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 'U-bis(3-amino-4-phenoxyphenylhydrazine)benzene, 3, 3-bis(3-aminost'oxy)biphenyl, 3,3-bis(4- Benzophenidyl, 4,4-bis(3-aminophenoxy)biphenyl, 4,4-bis(4-aminophenoxy)biphenyl, bis [3_ 23 200819501 (3-aminobenzene) Oxy)phenyl]ether, bis[3-(4-aminophenyloxy)phenyl]ether, bis[4-(3-aminophenoxy).phenyl]ether, bis & (4-aminophenoxy) Phenyl] scaly, bis[3-(3-aminophenoxy)phenyl]*one, bis[3-(4-aminophenyloxy)phenyl]one, bis[4_(3-amino-benzene) Oxy)phenyl]one, bis[冬(4-aminophenoxy)phenyl]one, bis[3-(3-amino-p-oxy)phenyl]sulfide, bis[3_('aminophenoxy) Phenyl]sulfinyl-, bis[4·(3-aminophenoxy)phenyl]f, ether, bis[4-aminophenoxy)phenyl]thioether, bis(3-aminophenoxy)benzene飒, bis[3-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-('aminophenoxy)phenyl Sulfone, bis[3-(3-aminophenoxy)phenyl]carbazide [> (4-amino)oxy]phenyl]methane, bis[4-(3-aminophenoxy)phenyl] A , bis[4-(4-aminophenoxy)phenyl]methyl, 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 2,2_bis[3- (4_ Aminophenoxy)phenyl]propane, 2,2-bis[(3-aminophenoxy)phenyl]propane, 2,2-biguanide (4-aminophenoxy)benzene J) Propane, 2,2"bis[(3-aminophenoxy)phenyl]-l,l,l,3,3,3-hexafluoropropane, 2,2-bis[3_(4-aminophenoxy) Phenyl]_1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(1aminophenoxy)phenyl]yi,3,3,'3_hexafluoropropane, 2 , 2_bis[4-(4-aminophenoxy)phenyl]·mm . hexafluoropropane, and the like. The diamine contained in the raw material of the quinone imine oligomer is cerium or two or more. Examples of the dibasic acid anhydride contained in the raw material of the imine oligomer include maleic anhydride, norbornene anhydride and the like. Alternatively, a compound which forms a benzene ring by three quantifications such as 4 24 200819501 ^^bU^pit ethynylbenzene) phthalic anhydride and 4-(2-ethynyl)phthalic anhydride may also be used. . The solvent contained in the raw material of the quinone imine oligomer is preferably an organic solvent. In the case of an organic solvent, it contains phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-nonylphenol, m-phenol , p-phenol, 2,3-dinonylphenol, 2,4-diphenylphenol, 2,5-xylenol, 2,6-diindol, 3,4-diindol, 3,5-di曱Phenol, N,N-dioxalylamine, N,N-dimercaptoacetamide, N,N-diethylacetamide, N,N-dimercaptomethoxyacetamide, N-dioxafluorene-2-indole: !: ketone, 1,3-dimethyl-2-sodium salindione, N-decyl caprolactam, 1,2-dimethoxy Ethane, bis(2-decyloxyethyl)ether, 1,2-bis(2-decyloxyethoxy)ethane, bis[2-(2-methoxyethoxy)ether, tetrahydrofuran 1, 1,3-dioxane, 1,4-dioxane, pyridine, picolin, dimethyl hydrazine, dimercaptopurine, tetramethylurea, hexamethylenephosphonamide, anisole and the like. These organic solvents may be used singly or in combination of two or more. In the raw material of the quinone imine oligomer, the solvent shown below may further coexist. In the organic solvent that can coexist, it contains benzene, toluene, "o-xylene, m-nonylbenzene, p-xylene, o-chlorophenyl, m-chlorotoluene, p-chlorotoluene, o-bromobenzene, m-bromobenzene , p-bromobenzene, chlorobenzene, bromobenzene, etc. The raw material of the quinone imine oligomer may also contain a catalyst for increasing the ruthenium reaction (described later), for example, an organic catalyst. In the case of an organic alkaline catalyst, it contains triethylamine, tributylamine, triamylamine, N,N-'dimethylaniline, N,N-diethylaniline, pyridine, α-picoline, β ·Picoline, 丫_Picoline, 2,4_二曱吼. Ding, 啥琳, 25 200819501 256U5pit isoquinoline, etc., ideally pyridine, γ-picoline. The content of the catalyst in the raw material of the material is not particularly limited as long as it can substantially increase the polymerization rate, and is, for example, 1 mol with respect to the tetracarboxylic dianhydride, and the content thereof is 0.001 to 0.5 mol. The step of producing the quinone imine oligomer includes (1) reacting a monoamine with a tetracarboxylic dianhydride, and then adding a dicarboxylic anhydride to continue the reaction' or (2) After adding a diamine and a dicarboxylic acid anhydride to react, a tetracarboxylic acid dianhydride component is added to continue the reaction, or (3) a diamine compound, a tetrasodium oxyacid anhydride, and a dicarboxylic anhydride are simultaneously added to cause a reaction. Steps, etc., may also be used in any of the steps. In the case of the quinone imine reaction, it contains hydrazine imidization, chemical hydrazine, and direct thermo-imidization. The raw material is synthesized at a low temperature below 1 〇〇, specifically, at -20 to 70 ° C, preferably at 〇 6 6 ° C to synthesize a quinone imine oligomer precursor, and then, the temperature is raised to I〇〇~2〇(rc is a method in which the oxime is imidized to obtain a quinone imine oligomer. The so-called chemical hydrazine imidization is chemically determined by using a hydrazine imiding agent such as acetic anhydride. The ruthenium imide precursor is subjected to a ruthenium imidization method. On the other hand, the direct hydrazine imidization is a mixture of a diamine, a tetracarboxylic dianhydride, and a dicarboxylic anhydride, followed by an organic base and/or Or rapidly increasing the temperature in the presence or absence of a solvent for azeotropic dehydration, directly causing the reaction system to produce a low S&imine A method for the imidization of a polymer precursor. The reaction time of ruthenium imidation depends on the type of monomer used, the type of solvent, the type of organic base catalyst, the type and amount of solvent for azeotropic dehydration, and 26 200819501 However, as far as the target is concerned, it is the case of j. Direct thermal brewing of imidization, in terms of the target, the water of the Germans reaches the theoretical amount (usually cannot be fully recovered,; 5 = rate). The reaction time is about several hours. In this case, one: the method of removing the water produced by the imidization by a co-agent such as toluene, and the method is quite effective.

For 44 hours, the reaction pressure of the imidization is usually not particularly limited, and usually it is atmospheric pressure = yes. The gf imidization reaction is usually carried out under an atmosphere of air, nitrogen, ammonia, atmosphere or argon, preferably in the atmosphere of nitrogen and chlorine of an inert gas, but is not particularly limited. The concentration of the monomer component contained in the low-molecular content of the hydrazine imine (polymerization degree) is particularly limited, but is generally about 1 〇 6 〇 % %. In the case of less than wt%, an extremely long reaction time is sometimes required, and in the case of exceeding the heart, there is a problem that the raw material is difficult to dissolve and the reaction efficiency is poor. The degree of polymerization is preferably from 20 to 50% by weight, more preferably from 3 to 4% by weight. The molecular weight of the quinone imine oligomer is the same as the molecular weight of the conjugated polymer of the group, and can be controlled by the molar ratio of the monomer component contained in the section. The original emission of the quinone imine oligomer is 1 mole relative to the diamine, and contains 〇.5 〇~ Please the four ugly dianhydrides of Moer are quite important, and it is better to contain (four) ~ ethical tetra- dianhydride Particularly preferred is a tetra-dianic anhydride containing 0. 50~ 〇·65 moles, preferably containing a G.50-0.60 mole. When it is produced by appropriately controlling the ratio of the monomer components, an yttrium imine oligomer having a desired molecular weight can be produced as described above. 200819501 256ϋ5ριί is a bismuth imide which is a bismuth acetal containing less than 二··············································· Therefore, it is not ideal. On the other hand, an increase in the molecular weight of more than • 0.80 moles 彳 会 will reduce the side of the plastic as a plasticizer, so it is not ideal. Further, the molar number of the dicarboxylic acid anhydride contained in the raw material of the imine oligomer Μ5 and the molar number 四3 of the tetracarboxylic dianhydride and the molar number of the diamine satisfy the relationship of the following formulas. (Μ4-Μ3) x2xl.〇^M5^ (Μ4-Μ3) χ2χ2.2 It is better to satisfy (Μ4-Μ3) x2xl.〇-M5S (Μ4—Μ3) χ2χ2·0 relationship, better to satisfy (Μ4 —Μ3) χ2χ1·〇^Μ5$ (Μ4—Μ3) χ2χ1·5 relationship; better to satisfy (Μ4—Μ3) χ2χ1·0^Μ5$ (Μ4-M3) χ2χ1·2. Μ(Μ4-M3) χ2χ1·〇> Μ5, the resulting quinone imine oligomer will leave an amine group, which will be colored when heated, and is not ideal in appearance. On the other hand, when (Μ4—M3) ><2x2.0<]V15, a large amount of bisinimide composed of a diamine and a dicarboxylic acid I anhydride is generated, and the amount of evaporation upon heating increases. ideal. The poly-S-imine resin composition of the present invention is characterized by comprising a repeating unit represented by the above formula (1-1) and a formula represented by the formula (1-2). The repeating unit of the polyimine resin and the quinone imine oligomer represented by the above formula (2). The polyimine resin may be either a hardened resin or a repeating unit represented by the formula (1-1) and a repeating unit represented by the formula (丨_2) when cured (polyamide). acid). 28 200819501

UbiDpir In the polyimine-based resin composition, the acid imine oligomer represented by the above formula (2) is 3 or more, more than 100 parts by weight, more preferably 100 parts by weight, based on the former. It is more than 90 parts by weight, and most preferably contains more than a part by weight and less than a part of r. When the light-weight lysine and the brewing imine oligomer are rotated, the "imine-based composition of the imine-based composition becomes charged = low" is used in the case of a metal laminate requiring low-temperature adhesion. use. Further, it is preferable to cure the composition of the polyamicimide resin to form a film and to reduce the brittleness. In the case where the polyimine-based resin composition of the present invention is cured and a laminate of a laminate for a printed substrate or a resin layer for a sheet is used, the glass transition temperature of the polysamino resin composition is 1 Torr. t above, 3 〇〇 < The following range n is better. Further, from the point of achieving the next low temperature condition, 100 to 240 c is preferable, and 1 〇〇 to 2 〇〇〇 c is more preferable. The polyilylimine-based resin composition of the present invention may contain any other thermal recording resin or the like without impairing the object of the present invention. - In the case of any thermoplastic resin, it contains polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polybutylene, polystyrene, polyvinyl acetate. ABS resin, poly Butylene terephthalate phthalate, polyethylene terephthalate s, polyphenyl hydrazine, polycarbonate, PTFE, celluloid, polypropylene oxime s to ether nitrile, polyamine, poly Hard, polyether oxime, polyether ketone, polyphenylene sulfide, poly-Sf light amine, poly-light amine, modified (tetra) benzene poly-imine. ^ In the case of any thermoplastic resin, it contains thermosetting polybutadiene formaldehyde resin, amine resin, polyurethane, enamel resin, SBR, 29 200819501 25605pif unsaturated polyester, 袅 袅 ^ ^ 醯 imide, etc. . For the purpose of knowing, #cyanate, phenolic resin, and polybamazet, the etchable resin may be alloyed by a suitable resin, a thermoplastic resin, or a thermosetting resin composition. The (iv) imine tree & is not particularly limited, and a conventional method can be applied. It is also possible to use various fillers or additives within the scope of the object of the present invention. In the case of filling "additional example 3, there are graphite, carbonized niobium, stone powder, molybdenum disulfide, fluorolipid, etc., etc. 耐%%% 一 匕 匕 性 性 性 性 性 η η η η η η η 二, magnesium carbonate, carbonic acid, etc., non-flammable 々曰6, clay, mica and other electrical property enhancers; asbestos, dioxide L, graphite and other leakage resistance enhancer; barium sulfate, dioxide, ash acid, acid resistance Increased transmission, zinc powder, antimony, copper powder hetero-conductivity enhancer; other _ fine beads, _ ball, talc, (four) soil, oxidation,, particulate soil,, hydrated oxygen, metal oxides, coloring materials and pigments, etc. . The mixing method is not particularly limited, and a conventional method can be applied. The polyamidene-based resin composition of the present invention may also comprise a polyaminic acid (an imine) containing a repeating unit represented by the above-mentioned (3_1)* and a repeating unit represented by the former parent (3_2). The precursor, and the polyphosphonium amide of the solution of the quinone imine oligomer of the above formula (2) are imidized, and obtained by reacting the quinone imine. The quinone imine (four) system polymerizes the terminal double bonds and polymerizes irreversibly. The polymer of the quinone imine oligomer can be detected by confirming the presence of a double bond by IR. In particular, when a coating film containing a solution of polyamidomic acid (bromoimine precursor) and a brewing imine oligomer is heated and dried to remove a silking agent, and it is hardened by reacting with an amine of 30 200819501 25605ριί, A film or layered polyimine-based resin composition can be obtained. The solvent containing the solution of the polyamic acid and the quinone imine oligomer is not particularly limited, but is preferably an aprotic polar solvent, more preferably an aprotic melamine solvent. Specifically, it can be exemplified by hydrazine, hydrazine-dioxime for meglumine, ν, Ν-dimethylacetamide, hydrazine, hydrazine-diethylacetamide, hydrazine, hydrazine: methyl methoxy acetamide Ν 曱 曱 曱 曱 曱 曱 咯 咯 咯 、 、 、 、 、 。 。 。 。 。 。 。 。 。. The viscosity of the solution containing the polyamido acid and the quinone imine oligomer is not particularly limited. For example, when an E-type viscometer is used in a range of 100 to 20,000 mPa · s in which the viscosity is measured, it is easier to control the coating thickness when the solution is to be applied. ι When heat-treating a solution containing a polyaminic acid and a quinone imine oligomer, a ruthenium imidization of polyamine and a reaction of the quinone imine oligomers occur, and the polyimine-based resin is cured. . The pressure of the heat treatment is usually sufficient as long as atmospheric pressure is used, but it can also be carried out under pressure. The ambient gas to be heat-treated is not particularly limited, and is usually air, nitrogen, helium, neon, or argon, and is preferably an inert gas of nitrogen and argon. Further, in the solution containing the polysilic acid and the brewing imine oligomer, an additive such as a catalyst may be added for the purpose of promoting or suppressing the crosslinking reaction by the heat treatment or controlling the reaction rate. Examples of catalysts include metal catalysts containing arsenic, antimony, indium or erroneous; transition metal catalysts containing tumbling, violent, nickel, money, cobalt, chromium, iron, copper, tin or platinum; and phosphorus compounds , hydrazine compounds, nitrogen compounds or sulfur compounds. Further, in the solution containing the polysilic acid and the quinone imine oligomer, irradiation of infrared rays, ultraviolet rays, α, rays, and the like, and electron beams and X-rays may be performed for the same purpose as 31 200819501 ^^OUDpll, and Plasma treatment or doping treatment.

The polyimine-based resin composition of the present invention can also form a film. In order to form a film, a solution containing a polyamido acid and a quinone imine oligomer is applied to a substrate, and the obtained coating film is desolvated and yttrium imidized to be hardened, and then peeled off from the substrate. Just fine. In the example of the substrate, an inorganic substrate such as a metal foil or glass, or a polymer film or the like is contained. Further, the application to the substrate may be carried out by using a coater or the like. The coating thickness is affected by the solids concentration of the solution containing the polyamido acid and the quinone imine oligomer, after the desolvation and the sub-monthly reaction (that is, the "hard domain") The film thickness of the cured resin is preferably 1 mm or less. Method of bathing and imidization (that is, "hardening") 3 = No _ ' As long as it is under reduced pressure, or in an inert atmosphere such as nitrogen, helium or argon: the lamp can be turned down. Further, it is sufficient to set the temperature of the solvent to be used at a temperature higher than the temperature at which the imidization reaction is carried out. For example, the use of an aprotic amine solvent is only a few. The imidization can be above. Desolvation and brewing are sufficient. The limit of the inch is usually 2 hours, that is, the metal layered body of the present invention contains a metal slab containing one or more layers of the gold continuum. Eucalyptus moon layer. One of the above layers of resin II / ^ & imine is the hardening of the composition of the composition (also known as 掏 formation of W Α ° metal laminated body wire with a good imine film, formed in «« amine. Single (four) double mosquito a surface layer and a layer of 200819501 25605pif on the square layer of the polylight amine layer; or the layer of the polyamidamine contacting the metal layer is hardened by the aforementioned polylight amine secret lipid composition of the present invention The resin layer is as described above, and the metal laminate of the present invention comprises one or more layers of a polyamic acid imide layer, and the fine layer above the ruthenium layer is formed by the polyacid imide system of the present invention. The cured product of the composition is composed of a layer of a polyacid imide resin layer having a thickness of #2 or more. Preferably, the adjacent layer is composed of a polyimine having mutually different compositions. The composition of the so-called polyimine is reduced. , means that the type and/or content of the monomer units are different. Further, at least the layer of the monoimine layer or the multi-layered polyimide layer of the plurality of layers may be composed of two or more layers. It is based on the secret of the mixture of the imine and the genus. The layer is a single layer. The layer of the layer is formed by the hardened material of the polyaniline resin composition of the present invention. In other respects, the layer of polyimine which constitutes the metal laminate is multi-voiced.接==亚:! A single-layer or double-sided multilayer poly' layer; the yttrium layer of the yttrium layer is a layer composed of the polyimide of the present invention = a sputum, a cured product of the product. In order to improve the readability with the metal ruthenium, it is preferable to contact the metal layer of the metal layer = _ _ lower. The above, 1 〇 _ = is more preferably 0·1 μηι or more, 5 μηι or less. : too = the thickness of the polyimine layer (single layer or multi-layer) of the metal laminate, :, the rigidity will be enhanced, and it can not be used for the need to bend and so on. 33 200819501 Restriction: The total thickness of the polyimine layer contained in the gold layer on b is preferably 3 or more, 75 μmη or less, more preferably 1 〇 or more, = good thickness in the above __, gold Riding the layer body and having 7 continuity, soft lasing, workbooks and low county tendency. ~, ', Barry Polyimide film $ as mentioned above, metal product The body may have a poly-imine film, a crucible, a single-sided or double-sided polyimide layer, and a metal layer laminated on the square or both sides. The ΐ ΐ 含 ΓΤ ΓΤ ΓΤ ΓΤ 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布Included with Optimex s, Optimex SG:: 克斯 SN (Ube Industries, Ltd. f, registered trademark / commodity private system aptonH, Kapton v, KaP_EN (Toray Dupont model 22 , registered trademark / trade name), Apieal AH, ApkaiNpi, fine (five), Zhu-style club kaneka system, registered trademark / trade name). In the case where the imine film of (4) is used in the above-mentioned laminated body, the thickness thereof is usually 3 or more, and 75_ = imine is in the range of .5 Å or more and 4 Å or less. Further, the above-mentioned polymer is formed by drying the non-thermoplastic polyimide, and the thickness thereof is G.l_ or more, and the thickness is not more than 5, and preferably less than 5 μΠΐ. More preferably 0.5, above, 16, or below. Metal layer "The metal layer contained in the layer is not particularly limited, and can be selected from copper 34 200819501 256ϋ3ριί and copper alloy, stainless steel Gansu; 5 Syrian eight steel and gold, nickel and nickel alloy (also Containing 42 alloy), sound. The metal layer of ^^ Temple, preferably a layer of copper or copper alloy, stainless steel can be formed by bonding a metal foil to a resin layer, and can also be used; x Ming polyimine resin The resin layer formed by the composition. The thickness of the metal layer contained in the m-layered body is not particularly limited as long as the metal laminate can be used as the thickness of the tape, and is usually 0·1_ or more and 150 μm or less. 2μιη or more, 丨m is tens, -, particularly preferably one or more, 3 or less, and the most sub-t3 = upper, 12μηη or less. Method for Producing Metal Laminate The metal laminate of the present invention does not impair the present invention The effect = the ground ginseng, the method for producing the metal laminate is not particularly limited. For example, it can be produced by the following method. (1) Heating and crimping a single layer or a plurality of layers of a polyimide film and a metal case Method 0 / (2) will be poly (four) (four) tree age The method of drying the varnish to form a layered body in the form of a metal layer as the outermost layer: (1) the secondary layered body U), and the following laminated body (1) or laminated body (ii the lipid layer is connected to each other) Method of laminating and laminating) ·, 'Layer body (1): A laminate having a metal layer only on the surface of only one of the heat-treated single-layer or multi-layered polyiminoimide film/menor foil. , 35 200819501 25605pif Laminates (11: r (4) Drying -=== Accumulation of paints The metal crucibles used in the manufacture of metal laminates are not particularly limited, and the metal foils of the conventional use are used. In the case of bismuth, it contains copper and copper alloys.

The alloy (also containing 42 alloy), Ming and Shaohe = the metal layer of the temple is preferably copper-alloy or non-axis. Metal sings only f:,: 乍 is the thickness of the tape, there is no particular limitation, usually above, 150_ or less, preferably 2 or more, 15 以下 or less, ^ good for 3 or more, 5 〇陴In the following, it is particularly preferable that the above is less than or equal to %, and that the range is lower than ΐ2μηι. To make a metal laminate: 'The surface of the gold Um yttrium can also be treated by electrocoagulation or corona discharge. And the method of adding the surface of the metal body of the present invention by using a metal roll or a metal roll coated with a rubber or the like, or a method of laminating between the rolls of the surface of the metal roll by rubber or the like. Or by using a hot press method or the like. The former is suitable for the manufacture of continuous roll products, and the latter is suitable for the manufacture of sliced loose articles, which can be suitably used depending on the application. ^ Further, the heating and crimping may be carried out in a gas atmosphere such as air, nitrogen or argon. The heating temperature requires a temperature above the glass transition temperature of the thermoplastic polyimine, preferably about 2 Torr above the glass transition temperature. The temperature above 〇 is 100 to 400 ° C, preferably 150 to 300. (: between the implementation can be. Also, the heating time is better than 01.01 seconds or more, 15 hours or less, heating 36 200819501 25605pif pressure as long as the Royal.l~„a seal can fly, hang ^5~ι〇ί^ Further, after the heat and pressure bonding, the post-treatment may be performed by an autoclave or the like for the purpose of further improving the adhesion of the metal laminate. The post-treatment is carried out under the following conditions. The post-treatment temperature is usually 15 Torr. ~ 4 〇〇 it, for 2 (8) ~ ^:, at _ between: minutes ~ 5 〇 hours, the pressure is normal ^ ~ 3MPa consumption. The South pressure dad device is preferably vacuum or replaced by nitrogen or gas, to Oxidation of the metal foil is prevented. In the case of the method for producing a metal laminate of the present invention, in the case of a varnish (containing a polyacid imidic acid) of the surface resin composition (a solution of a polymer), a roll can be used. Coating machine, port '= machine, gravure coater, dip coater, spray ς ==, strip coater, etc. General coating device = suitable for β-viscosity and coating thickness The earth (4) sub- (four) resin composition is coated with hot air or electric heating by electric heating or oil heating. Suitable for the purpose of discoloration caused by oxidation of the metal box, must be deteriorated, and the external ':: nitrogen, argon or hydrogen gas instead of dry ambient gas can be coated with air after the coating of the polyimine resin composition, =: 60~6 The temperature of the temperature is better when the drying is carried out by the coating film. Therefore, it is possible to prevent the film thickness from being uniform: =: or the surface of the film is uneven. # / The better dimensional stability of the tree is better than the formation of the 妒 胲 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Then, the sheet has a resin film and a hard layer formed on the early or both sides of the tree of the present invention. The so-called tree, can be exemplified by the resin of the tree of 2, which is good for the material. Acid imine film. There is no (4) limitation on the method of forming a resin layer on the resin film. The method of manufacturing the metal laminate is shown by the coating and drying of the varnish just described. (4) Resin composition [Examples] Hereinafter, according to Examples and Comparative Examples, The invention is not limited by the scope of the invention. In the examples and comparative examples, the evaluation of the poly-proline is determined according to the following method: logarithmic viscosity (rjinh): The acid varnish was added to the mercaptoacetamide solvent, and the solid content was adjusted to 0.5 years old, and then measured in a thermostat set at 35 ° C. 2) E-type viscosity · · E-type viscometer (r〇1〇5A, Toki Sangyo Co., Ltd.) was measured at a temperature of 25 ° C under a condition of 3. Cone rotator. Evaluation of yttrium oligomers Ο logarithmic viscosity (riinh) · • The amine oligomer was added to the n,N-dimercaptoacetamide solvent, and the solid concentration of the quinone imine oligomer was adjusted to 〇·5 g/dl. Further, the solution was adjusted to 35 ° C to measure the logarithmic viscosity. 38 200819501 25605pif 2) Molecular weight (weight average molecular weight Mw, number average molecular weight Μη): GPCsystem-21H series manufactured by Shodex Co., Ltd. (Detector: RI, extended catalyst: tetrahydrofuran, flow rate: 1 ml/min, column temperature : 40 ° C) was measured. 3) Glass transition temperature (Tg): The product was measured under a nitrogen-containing atmosphere using a DSC60 series of a thermal analysis device manufactured by Shimadzu Corporation. Evaluation of the composition of the polyimine-based resin 1) The glass transition temperature (Tg): It was measured under a nitrogen-containing atmosphere using a thermal analysis device DSC60 series manufactured by Shimadzu Corporation. 2) Desmear speed: The polyaminic acid solution was coated on a glass plate, and a polyimide film was prepared by heating at 30 °C for 4 hours under a nitrogen-containing atmosphere. Cut and remove 6x2 cm2. The sample of the size was used as a sample for measurement. The etching solution was prepared by mixing 50 g of MACUDAIZAR 9275 (manufactured by Japan's MacDermid Co., Ltd.), 50 ml of MACUDAIZAR 9276 (manufactured by MacDermid Co., Ltd.), and ion-exchanged water to a total of one liter. The sample was immersed in the etching solution for 15 minutes, rinsed, dried, and the desmear speed was calculated from the change in weight before and after the dipping. 3) Volatility: 1 part by weight relative to the polyglycolic acid solid portion 33 parts by weight of the quinone imine oligomer was added to the polyamic acid varnish to prepare a solution, which was cast onto a glass substrate. The film obtained by heating at 24 ° C for 15 minutes under a nitrogen-containing atmosphere was peeled off and cut into 5 cm square. The film was placed in a glassware, and heated at 280 ° C for 30 minutes under a nitrogen-containing atmosphere, and then cooled to room temperature. The amount of precipitates adhering to the lid of the glassware was visually observed, and evaluated based on 〇 (no 39 200819501 25605 pif precipitates), Δ (slightly precipitated), and X (almost completely precipitated). Evaluation of metal laminates 1) Peel strength: measured according to jISC_6471. Prepare a length of 5〇 mm and width parallel to the flow direction of the foil! The sample of mm is at 23. 〇, relative

The metal foil was placed at an angle of 9 in an environment of a humidity of 50%, and peeled off from the insulating layer at a peeling speed of 5 〇 mm/min, and the stress was measured. 2) Solder heat resistance temperature: according to IPC-TM_650 (The institutefe

InterC()nnecting and Packaging Electronic Circuits ) N 〇·2·4·13 determination. At 24 rc to 34 (every 1 〇 between rc, the maximum temperature at which no expansion and metal-polyimine interface discoloration occurs as the solder heat temperature. The sample is used in an environment of 8 VC and 85% relative humidity. The sample was stored for 48 hours. The chemical structure was confirmed by a nuclear magnetic resonance (NMR) apparatus ΕΧ 4 (10) manufactured by JEOL Ltd. The solvent, diamine, and tetrazoic acid used in the examples and comparative examples were used. The abbreviation of dicarboxylic anhydride is as follows: — 1) Solvent: DMAc : Ν, Ν-dimethylacetamide 2) Diamine: ΑΡΒ : 1,3-bis(3-aminophenoxy)benzene, APB -R ··1,3-bis(4-aminophenoxy) stupid, m-BP: 4,4'-bis(3-aminophenoxy) phenyl, 200819501 25605pif 3) tetracarboxylic dianhydride BTDA · 3,3',4,4'-benzophenone tetracarboxylic dianhydride, DSDA: bis(3,4-dicarboxyphenyl)sulfonic acid dianhydride, ODPA: bis(3,4-dicarboxybenzene Ether dianhydride, BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride, PMDA: pyromellitic dianhydride, 4) Dicarboxylic anhydride: MA: maleic anhydride NDA: norbornene Alkene anhydride [Synthesis Example 1-1] Synthesis of polyamic acid varnish In a vessel having a stirrer and a nitrogen introduction tube, DMAc (991 g) was charged as a solvent, and then APB (146.25 g) and APB-R (61.39 g) were placed therein, and the mixture was stirred until dissolved. Next, btda (219.92 g) was poured in, and the mixture was stirred at 50 c for 6 hours to obtain a polyamic acid varnish. The obtained polyamic acid varnish obtained by polyamic acid glutamate. The secret is reduced, the pit + modulation = = [Synthesis Example 1-2~M5] except for the change of the type of acid dianhydride and diamine The synthesis of the polyamic acid in the same manner as in the synthesis example is shown in Table 1 together with the synthesis example 1. Will... fruit 41 200819501;

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s/IPcrVNa] qu{U <Ν an OCNCN — moooc — ΟΝΟΟΟΟ Όν〇ν〇^〇Ό〇〇ιη〇ΊΓη — inch... 0000000(Ν0000000 〔oUI/oal] a+u/a+v om/om] α/υ 005s6ds/0 e 丨CQdv I 000CP6O iFe-OQdv SdV 009I/P60 iFΉώίίν mdv ooos 卜 60 iFβώΟΗνDQdv 000 I/P60 iFΉ-sv sv 000 10680iF>J>3dV mdv 000 1/5 inch 60e-PQdvPQdv 000 1/ 000 1 iFΉ-CQdvCQdv 000·ί/ς66Ό s e-advCQdv 000·Ι/ς66Ό iFβ-PQdvOQdv 000 IS6 0 01/0 βώα-ν I 000·Ι/ςΑ6Ό ς/ς e-gdvmdv 000 s Bu 60 1/6 ^«£< sv 009I/S660/01 IPQdv 000cSA6di!L Ήώ€ίν mdv

/IV J!ds9s [om/om] a/v fe 01/0 01/0 Ui inch/9 (n/8 0/01 0/01 0/01 0/01 0/01 0/01 0/0 ΐ 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 ΖτΙ 9丨1 彳一tI £丨1 <Ν丨II丨一200819501 256U5pif [Synthesis Example 2-1] Synthesis of quinone imine oligomers in J has a mixer, nitrogen introduction tube, extractor, cooler and In the k bottle, APB (29.23g, 〇1〇m〇1), 〇DpA (15 〇, 〇5Π^, maleic acid liver (hereinafter referred to as MA) (11.77g, 0.12m〇1), $

DMAc (132g) as a η] and 曱 (42g) as a dehydrated azeotropic solvent. . Thereafter, the solution was stirred and heated to 130 + - 135% while passing nitrogen gas. At the same time that the internal temperature reaches 13 (the vicinity of rc, the steaming of water and water is caused. After the part is condensed by a cooler and the water is separated from the benzene by the extractor, only the toluene is returned to the system, and A part of the nitrogen gas is distilled from the upper part of the cooling pipe to the outside of the system at the same time. After the reaction for 7 hours, the reaction vessel is cooled to stop the polymerization reaction. After the reaction mixture is charged in methanol to precipitate the ruthenium oligomer, This was washed with decyl alcohol, and then dried under a nitrogen atmosphere for 9 hours to obtain 39.59 g of a quinone imine oligomer (yield 78%). The logarithmic viscosity of the substance is 〇.〇7dl/g, the average molecular weight (hereinafter referred to as Μη) measured by GPC is 2100, and the weight average molecular weight (hereinafter referred to as ^^¥) is 3100, and the dispersion of the molecular weight distribution index is ] ^^ Ship 11 is 1.5. In order to confirm the structure of the obtained quinone imine oligomer, it can be confirmed by NMR and FD-MS that the brewed imine oligomer having the desired structure has been produced. The Tg of the sub-private oligomer has a Tg of 118 ° C. The brewing imine oligomer is at a concentration of 4 0 wt% was mixed with DMAc at room temperature, and it was rapidly dissolved. [Synthesis Example 2-2 to 2-7] 43 200819501 25605pif In addition to the modification of the type of tetracarboxylic dianhydride and diamine, it is shown in Table 2. The synthesis and evaluation of the quinone imine oligomer were carried out in the same manner as in Synthesis Example 16. The results are shown in Table 2 in the same manner as in Synthesis Example 2-1. • [Synthesis Example 2-8] The mixer and the nitrogen introduction tube were provided. In a flask of extractor, cooler and thermometer, APB (29.23 g, 0.1 mol), 〇DPA (15 51 g 0.05 mol), NDA (9.85 g, 0.06 mol) and DMAc' P (163 g) as a solvent were charged. The resulting solution is heated to the side while passing nitrogen gas. While the internal temperature reaches 160 ° C, a small amount of DMAc and water evaporation occurs. One part of the condensate is condensed by the cooler to the extractor. The mixture was withdrawn and a portion of the nitrogen gas was distilled from the upper portion of the cooling tube to the outside of the system. After 2 hours, NDA (9.85 g, 0.06 mol) was charged into the reactor and heated for another 4 hours. Thereafter, the reaction vessel was cooled. The polymerization reaction was stopped. The reaction mixture was charged in methanol to precipitate the ruthenium oligomer. After that, it was washed with decyl alcohol. Thereafter, the G washing material was dried at 9 ° C for 12 hours under a nitrogen gas flow to obtain 41.81 g of a quinone imine oligomer (yield 73%). The logarithmic viscosity dl/g of the quinone imine oligomer, the number average molecular weight Mn 1500 measured by GPC, the weight average molecular weight Mw is 2100, and the polydispersity of the molecular weight distribution index. The structure was confirmed by NMR and FD-MS to confirm that an imine oligomer having a desired structure was produced. The Tg of this quinone imine oligomer was determined to be 120 ° C by DSC. The quinone imine oligomer was mixed to DMAc at a concentration of 40% by weight at room temperature to rapidly dissolve the solution of 200820081501 2560$pif. [Synthesis Example 2-9 to 2-14] Synthesis and evaluation of the quinone imine oligomer were carried out in the same manner as in Synthesis Example 2-6 except that the type of the tetracarboxylic dianhydride or the diamine was changed as shown in Table 2. . A summary of the results is disclosed in Table 2. [Synthesis Examples 2-15 and 2_16] The synthesis of bis-imine was carried out by a method described in JP-A-H07-99764. A summary of the results is disclosed in Table 2. 45 200819501

JiQ-tr) 09lo<N Ren

Ms i 51pcrvi] lcju [3. 〕 ^ Ν τ—< ^―-i 1—^ ^―ί. Τ—^ τ—^ r—Η r—Η ^ρ—<009<ν 009(ν 0§ I 0081 oi 001<Ν 009£ 009ΓΠ οοςΓη οος(Ν 008CNI οοοοΓΝι ΟΟΙΓη 0061 0081 0081 I 00 inch ί 00 inch I 00 inch <Ν ooerNI οοεΓΝΙ 00 Bu 千ΓΝ1 000<Ν 00Ι(Ν 600 800 800 i 00 900 i 800 800 0000 900卜 ΖΌΌ i £1) Ο I sl) 081 8£ί 6U ooel lCNl s I (Nl § 6U 6U 9U (NiNI <N(N1 l(NI ocu 0 0

VM VOM VON VON VOM VON VOM VOM VON VIMvsvs vs VPMvs VPM sv OQdvde_s PHa丨 jg-m sv svaPHv sv dCQ丨 sdm-s s丨 sv PQdv sv rndv vom vas vdQo vasPH vsa vais vdao valm vas vso v_d vais vadOQ vdao

91 丨(N tnI 丨<N inch T<N ει 丨<N (NI 丨(N Π·(Ν 01 丨<N 6—(n 00丨<NL,z 9丨3 a 丨< N inch 丨<N sz丨τ I 丨<N 200819501 25605pif [Example 1] In a flask equipped with a stirrer, a nitrogen introduction tube, and a thermometer, the polyamic acid varnish obtained in Example 1-1 was placed. The acid imine oligomer obtained in Synthesis Example 2-1 was contained in an amount of 33 parts by weight based on the weight fraction of the polyamic acid in the polyamic acid varnish. The DMA c was mixed at 40 ° C and mixed to obtain a pale brown transparent solution having a viscosity of 100 to 1000 in the e-type viscosity leaf. The film obtained by casting the obtained solution had a Tg of 177 ° C. According to the above procedure, the degreasing speed was 2 ug/cm2/min, and the volatility test was evaluated as 〇. Next, the commercially available polyimine resin film (Dolly DuPont Co., Ltd., trade name: On both sides of Kapton 100EN), the above solution was applied by a roll coater, and dried at 70 ° C for 5 minutes, l〇〇t: dry 2 minutes, 140 C dry 2 minutes, 180 ° C dry 2 Points, 220 ° C to dry 1 dryness, and the thickness after drying is 4 μm. Thus, a polyimide film having a double-layered polyimide composition of a resin film is obtained. The copper foil (manufactured by Furukawa Circuit FoH Co., Ltd., trade name) ···、厚9μηη) directly laminated on the obtained polyimine-based resin cured layer of the insulating film, and using a roll-type laminator coated with Shishi rubber, under conditions of 240 C and a pressure of 1.4 MPa After that, it is annealed with a batch of high-pressure argon at a temperature of 3f ° C and a nitrogen-containing atmosphere for 4 hours, and the imide metal laminate is used. The temperature is 3 boots. [Examples 2 to 29] 47 200819501 25605pif, except that the types of polyamic acid varnish and quinone imine oligomer are changed to those of Table 3A or Table 3B, and Examples 丨Similarly, the synthesis and evaluation of the polyamidene-based ruthenium composition were carried out, and the lysine metal laminate was fabricated and evaluated. The results are disclosed in Table 3A or Table 3B. [Comparative Example 1]

- The synthesis and evaluation of the composition of the life imine resin composition were carried out in the same manner as in Example 1 except that the quinone imine oligomer was not used, and the polyimine metal laminate was produced and evaluated. The results are disclosed in Table 3A. [Comparative Examples 2 and 3] The acid imine was applied in the same manner as in the Example except that the type of the polyamic acid varnish and the diacid having the crosslinkable group-containing additive was changed to those shown in Table 3B. The evaluation of the composition of the composition of the composition, the production and evaluation of polyimine metal laminates. The results are disclosed in Table 3B.

48 200819501 f J!ds9s [νε ί solder resistance temperature rc ) 340 340 340 340 300 340 340 300 320 300 330 320 300 290 〇 On (N 300 320 peel strength [kN/m ] 0000000000^00000 » • Pan” * »··«*··« r—^ r—Η τ—H f—^ τ—^ r—^ (N 〇OC 〇Ο 1 Volatile test〇〇〇〇〇〇〇〇〇〇〇〇〇〇 〇〇< Desizing speed [pg/cm2/min] ? \ 1 i inch ^ V \_f 177 168 172 196 205 182 172 185 165 155 180 182 186 190 cn Ο (N 〇0\ IT) ^ Η % ^ Smart side 100/33 100/33 100/33 100/33 100/33 100/33 100/33 100/33 100/33 100/33 100/33 100/33 100/33 100/33 100/0 100 /11 100/150 Formula 1 (2) 1 rH τ—Η τ—^Η τ—Η τ—Η ι—Η τ—Η τ—Η r—^ τ—Η r—Η rH τ—Η 1 ,丨1 1 < r~H 醯imino oligomer Synthesis Example 2-1 Synthesis Example 2-1 Synthesis Example 2-1 Synthesis Example 2-1 Synthesis Example 2-1 Synthesis Example 2-1 Synthesis Example 2-1 Synthesis Example 2 -1 Synthesis Example 2-1 Synthesis Example 2-1 Synthesis Example 2-1 Synthesis Example 2-1 Synthesis Example 2-1 Synthesis Example 2-1 1 Synthesis Example 2-1 Synthesis Example 2-1 Polyamine Synthesis Example Synthesis Example 1 2 Synthesis Example 1-3 Synthesis Example 1-4 Synthesis Example 1 - 5 Synthesis Example 1-6 Synthesis Example 1-7 Synthesis Example 1-8 Synthesis Example 1-9 Synthesis Example 1-10 Synthesis Example 1_11 Synthesis Example 1-12 Synthesis Example 1-13 Synthesis Example 1-14 Synthesis Example 1-15 Synthesis Example 1-1 Synthesis Example 1 - 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative Example 1 Η τ «·Η 6 inch 200819501 [.]ir?i[ S/S] _| [.££/p5/3ZL] [.] [Jade ¥ side] Review ftifg / get dyed one by one ^ 鍩 龄 inch inch inch inch inch inch inch inch inch inch inch inch inch •ο • »»»#· ··»«♦» » , 丨· ! ( gas I ( ψ i < , — i' < v-丨 — f 崎 f H t_ 1 i 〇〇〇〇〇〇〇〇〇〇〇〇〇τ τ τ τ ζ τ ζ τ τ ζ e τ ζ

Inch 001 ΖΟΟΙ <ΝοοΙ ZL\ S 6 Buyi LLA ecoI 181 oool oz/i PI eil eil §oi §οϊ §01 §01 eil eii iol iol rnsoi §01 1

./IV J!ds9s [S <] Η·(Νί#^φ U 丨<Νί4^φ <Νϊ-(Νί4^φ π-(Νί#^φ Οΐ 丨(Ν^^φ 3 OC丨(Νί#^φ ΖΓΓΝΙί卷哒命9 丨<Νί#^φ ς 丨<Νί4^φ inch丨2:苳哒^ 3 ϊ丨I冢哒命1丨1 ί#^φ I丨I ίφ^ Φ ϊ 丨ίί4^φ 丨 丨一ί#^φ ι 丨u#^4 I丨一ί#^φ I 丨I ί4^φ I丨I leather 哒 I丨一ί4^φ I 丨ϊ^^φ Ϊ丨I ί4^φ 6<Nf#^_ ocrsli# Marriage #9<Ni#^·sf#德(四) 寸(Nf杳键^ eCNIf在衮# <N(Nf#^· ιΓΝΙί冬嫁取宕苳衮# 61 strikes to take 81 leather to take ZJi#

Γ inchΓηs X τ d 8— ο 9Ι·<Νί4^<πΙ-ΙΜ5Φ^ si ο芝__5 X τ 091 81/001 0 ςΙ-<Ν¥^φΙ-Ι ί#^φ^ SS 200819501 25605pif As shown in Table 3, it was found that the metal laminate produced by using the resin composition containing no quinone imine oligomer (Comparative Example 1) had poor peel strength. Therefore, sometimes the performance as an adhesive is insufficient. Further, it can be seen that the resin containing bisinimide to replace the quinone-amine oligomer has a poor evaluation result of the volatility test of the products (Comparative Examples 2 and 3), and is exposed to a high temperature environment as part of the composition. (Thinking to be a bismuth imine) There is a sublimation.

On the other hand, as shown in Examples 1 to 14, the evaluation of the H-pole of the resin composition containing one of the polyamic acid varnishes of the synthesis examples M to 1 to 14 and the quinone imine oligomer was carried out. Higher, using the metal laminate produced by this, the peel strength is also quite sufficient. χ, as shown in Examples 15 and 16, the ratio of the amount of the amide group to the quinone imine oligomer is not the same, and the Τ/酉: subtropical tree 曰 composition of the present invention exhibits excellent physical properties. However, when the poly-proline acid solid-shaped wound is less than the south (the yttrium oligomer is too small), the peel strength is inferior, and when the amount of fe-imine oligomer is too high, the evaluation of the volatility test is lowered. After that. Further, as shown in Examples 17 to 29, the evaluation of the volatility test of the resin composition containing one of the polyaminic acid and the quinone imine oligomer of Synthesis Example 2-2 is also high, and the use thereof is also high. The stripping strength of the fabricated metal laminate is also quite sufficient. [Industrial Applicability] The composition of the polyimine-based resin of f-Ming can be used for heat-resistance, blame, and refractory. [Description between the schemas] Benefit 51 200819501 25605pif [Key component symbol description] Benefit / η,

Claims (1)

200819501 25605pif X. Patent Application Range: 1.- Polyimine-based resin composition, the system comprising the repeating unit shown and the heavy-duty yoke shown in the general formula (1·2), and下_式(7)科科-Amine oligomer 1 〇〇• · (l'l) • · . (1'2) ΛΛ 1-ΝΥΒΥΝ" 〇〇〇〇-α2~ν^β^ν-Π fl 〇 〇[, in the formula (1·1) and the formula (), A]AA2 are the same as the following formula (ai), and may be different as the following formula (10) or (b2)' ΟΛ YO I οα^πηο onnA- WKNO N I Z ΟΛ YO N (2) 53 200819501 25605pif ' [In the formula (2), A3 is one of the following formulas (cl) to (c4), and b3 is one of the following formulas (dl) to (d4), and z is the following formula (£ΐ) or (e2) ), 1 is an integer from 1 to 5] [In the formulas (cl) to (C4), 乂7 to 12 are selected from the group consisting of single bonds 0-, -S-, -CO-, -COOs, -c (CH: NHC0~, which are mutually identical) , c (cf3) 2 one, — so: can also be different] • · · (dl) • · · (d2) [In the formulas (dl) to (d4), Y7~12 are selected from the group consisting of (d4), -s-, -CO-, -COO~, a c (ch3) _ 54 200819501 25605pif -NHCO~ , they can be identical to each other, c(cf3)2---s〇2- can also be different] [In the formula (el) or (e2), the 仏~4 series is selected from the group consisting of a hydrogen atom, a 3-atom atom, and a carbon number of 3, which may be the same as each other, or a R5 system of 0-, -S-, ~CH2~, -C(CH3) 2—, —CO — or —c〇〇—]. The private (IV) sub-(four) resin composition as described in the first item of the first aspect of the invention, wherein one of the Al and the general formula (1_2) of the above formula (H) is (al) and the other is (a2). 3. The patent of the pro-Asian (four) resin as described in the above-mentioned patent, wherein the above-mentioned general formula (7) is taken as 4. The poly-imine resin composition as described in the scope of the patent application is not. In the above, the quinone imine oligomer represented by the above formula (2) is contained in an amount of 5 parts by weight or more and 1 part by weight or less based on 100 parts by weight of the polyimine resin. 5. The polyimine-based resin composition according to claim 1, wherein the glass transition temperature of the polyilylimine-based resin composition is 10 ° C or more and 300. 〇 The following range. 6. The polyimine-based resin composition of claim 1, wherein the A3 B3 is selected from the following formula (d1) and (d5)~ or (e4), 1 is an integer of ι~5, and is a group of (c5) or (C6), (dlO), and z is (e3) [The definitions of R3 and R4 are the same as those of the above formula (e2)]. - 7. A mixture comprising a repeating unit of the repeating unit represented by the following formula (3_2) represented by the lower riding type (3_υ), and the acid imine represented by the formula (2) is low. Polymer and solvent if necessary 56 200819501 25605pif II Ο Ο 11 •Α如;^一Βι Η〇ΐί Γ〇Η 〇〇II Ο Ο II Η〇Ίί Ι~〇Η 〇〇(3-1) • · · (3-2) Γ [In equation (3-1) and 〇υ, Α] and ^, or (a2), they can be identical to each other, or they can be displayed in the same way as Ul (Μ) Or (b2), they can be the same as each other, and they can be different from each other. • · · (a2) • (al) 〇〇 ΛΑ ·Α3 - ΝγΒγΝ-Ο 0 (bl) (b2) 〇Aζγ 〇 [In the formula (2) is the above formula (dll·1 is an integer of 1 to 5) z onnA VHO NIA^o is one of the middle d4 (2) 逑 (cl) to (C4), B : —, Z is the above formula (ei) or (e2), (cl) -Ο— 57 200819501 25605pif (c2) x8""^^Xicrl丨- χιΗ卜士X12 (c3) (c4) [In the formulas (cl) to (c4), X7~]2 are selected from the inclusion of a single bond, -ο-, -S-, -CO-, -COO-, _c (CH3), -c (CF3) 2—, — S〇2-, —NHCO-jun, can be the same or different (el) (e2) [in the formula (el) or (e2), 'R; [~4 is selected from the group consisting of a hydrogen atom, a halogen atom and an alkyl group having a carbon number of 1 to 3, which may be identical to each other, Differently, R5 is a 0---S---CH2-. -c (CH3) 2___ Co- or - COO-]. 8. A method for producing a cured polyimine-based resin, which comprises the step of reacting a mixture described in the seventh item of the Γ π patent range to form an imine.五 imine; (5) The second application of the patent application, the 1st metal laminate, which comprises a metal layer and a resin layer, and the first 58 200819501 256U5pit resin layer of at least _ layer is made by Ruiya The hardening of the amine-based composition of the composition of the amine-like layer 4::;:: genus: sub-layer, and layered in the aforementioned (four) (four) layer of the money layer is difficult layer , the resin of the (IV) imine-fat composition described in the series? The sheet has a resin film, and a resin layer composed of a cured product of the above-mentioned, early or double-sided composition of the patented amine resin composition. , t / 59 200819501 25605pifl.doc imide oligomer represented by the formula (2) is provided. The polyimide includes repeating units represented by the formula (1-1) and the formula (1-2). 〇〇• A Λ --- --.-(1-1) N-f ΟΛΒνο OAVO OAYO - fA3 A2t IN ΟΛΖΥΟ Z 0AYO NI A3 VII. Designated representative figure: (1) The representative figure of the case is: no (2) The symbol of the representative figure is simple Note: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 〇〇(1-1) Λ Λ •A1—\BlrN_ 〇〇〇A\o ΟΛ ¥0 NI A2 OAVO OAYO NI A3 OAVO z OAYO NI A3 (1-2) (2 4