KR101077405B1 - Laminate for wiring board - Google Patents

Abstract

It has high heat resistance, low moisture absorption and excellent dimensional stability. It does not involve various problems originating from the adhesive layer and suppresses warpage due to humidity. Furthermore, the difference in humidity expansion coefficient in the TD direction and the MD direction is small and there is no anisotropy in the plane. A laminate for wiring boards having a polyimide resin layer serving as an insulating layer. The wiring board laminate has a metal foil on one side or both sides of the polyimide resin layer, and at least one layer of the polyimide resin layer is 2,2'-dialkoxybenzidine or 2,2'-diphenoxybenzidine. It consists of 10 mol% or more of polyimide structural units obtained from tetracarboxylic anhydride.

Wiring board laminate, polyimide resin layer, thermal dimensional stability

Description

Laminated body for wiring board {LAMINATE FOR WIRING BOARD}

The present invention is a laminate for wiring boards used in flexible printed wiring boards, HDD suspensions and the like.

In recent years, high performance, high functionality, and miniaturization of electronic devices have been rapidly progressed, and accordingly, demands for higher density and higher performance have also increased for electronic components used in electronic devices and substrates on which they are mounted. Regarding the flexible printed wiring board (hereinafter referred to as FPC), thin wire processing, multilayer formation, and the like have been performed, and the thinning and dimensional stability of the material constituting the FPC have been strictly demanded.

Generally, the film which consists of polyimide resin excellent in various characteristics is widely used for the insulation film of FPC, The epoxy resin and acrylic resin which are excellent in low temperature workability are used for the insulation adhesive layer between an insulation film and a metal. However, these adhesive layers have a problem of causing a decrease in heat resistance and thermal dimensional stability.

In order to solve such a problem, in recent years, the method of coating and forming a polyimide resin layer directly on a metal, without forming an adhesive layer, has been employ | adopted. Japanese Patent Application Laid-open No. Hei 6-93537 discloses a method of providing an FPC having excellent adhesion and thermal dimensional stability by multilayering a polyimide resin layer into a plurality of polyimides having different thermal expansion coefficients. However, since these polyimides have high hygroscopicity, problems such as expansion when immersed in a solder bath and poor connection due to dimensional change after moisture absorption during thin wire processing are caused, and in general, metals used for conductors have humidity. Since the expansion coefficient is close to zero or zero, the dimensional change after moisture absorption also causes defects such as warpage, curl, and torsion of the laminate.

Prior literatures related to the present invention include the following documents.

Patent Document 1: Japanese Patent Publication No. Hei 6-93537

Patent Document 2: Japanese Patent Application Laid-open No. Hei 2-225522

Patent Document 3: Japanese Patent Application Laid-Open No. 2001-11177

Patent Document 4: Japanese Patent Application Laid-Open No. 5-271410

From these backgrounds, the demand for FPC which consists of polyimide resin which has the outstanding low hygroscopicity and post-moisture dimensional stability is increasing recently, and the improvement examination of the polyimide used for it is performed variously. For example, Japanese Patent Laid-Open Publication No. Hei 2-225522 and Japanese Patent Laid-Open Publication No. 2001-11177 propose polyimide that improves hydrophobicity and exhibits low hygroscopicity by introducing a fluorine-based resin. And a disadvantage that adhesiveness with a metal material is bad. As for other measures of low hygroscopicity, as shown in Japanese Patent Application Laid-open No. Hei 5-271410 and the like, low hygroscopicity was not realized while retaining good characteristics of polyimide such as high heat resistance and low thermal expansion coefficient.

On the other hand, the polyimide has a structure in which a dicarboxylic acid component and a diamine component are alternately bonded, and a polyimide using diaminobiphenyl or diaminobiphenyls substituted with methoxy as a diamine is disclosed in Japanese Patent Application Laid-Open. Although it is illustrated in 2001-11177 and Unexamined-Japanese-Patent No. 5-271410, the specific example is not shown and what kind of characteristics they have cannot be predicted.

Accordingly, an object of the present invention is to provide a laminate for wiring boards having a polyimide layer which solves the above problems and has excellent heat resistance, thermal dimensional stability and low hygroscopicity.

This invention is a laminated body which has metal foil in the single side | surface or both surfaces of a polyimide resin layer, WHEREIN: At least 1 layer of the said polyimide resin layer contains 10 mol% or more of structural units represented by following General formula (1). It is a laminated board for wiring boards characterized by the above-mentioned.

(Wherein, Ar ₁ is a tetravalent organic group having at least one aromatic ring, R is a hydrocarbon group having 1 to 6 carbon atoms.)

The laminate for wiring boards of the present invention has a structure in which metal foils are laminated on one or both surfaces of one or multiple layers of polyimide resin. At least one layer of a polyimide resin layer contains 10 mol% or more of the structural unit represented by the said General formula (1).

In the structural unit represented by General formula (1), Ar <_1> is a tetravalent organic group which has one or more aromatic rings in a formula, and the aromatic tetracarboxylic-acid residue which arises from aromatic tetracarboxylic acid, its acid dianhydride, etc. It can be said. Therefore, Ar ₁ is understood by explaining the aromatic tetracarboxylic acid to be used. Usually, when synthesize | combining the polyimide which has the said structural unit, since aromatic tetracarboxylic dianhydride is often used, preferable Ar <_1> is demonstrated below using aromatic tetracarboxylic dianhydride.

As said aromatic tetracarboxylic dianhydride, it does not specifically limit but a well-known thing can be used. Specific examples include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 2 , 3,3 ', 4'-benzophenonetetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride Water, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic acid Dianhydrides, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2, 3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1 , 4,5,8-tetracle Ronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetra Carboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -p-terphenyltetracarboxylic dianhydride, 2,2 " , 3,3 "-p-terphenyltetracarboxylic dianhydride, 2,3,3", 4 "-p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxy Phenyl) -propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1- Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8,9-tetracarboxylic dianhydride, Perylene-3, 4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenane Tren-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic acid Dianhydrides, 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'- oxydiphthalic dianhydride, etc. are mentioned. In addition, these can be used individually or in mixture of 2 or more types.

Among these, pyromellitic dianhydride (PMDA), naphthalene-2,3,6,7-tetracarboxylic dianhydride (NTCDA) and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride Preferably selected from (BPDA). In particular, in order to realize a low thermal expansion coefficient, it is preferable to use PMDA or NTCDA. By mixing and using a suitable quantity of BPDA to this, it can adjust to the thermal expansion coefficient of the same grade as a metal foil, and can adjust to the value of 20 ppm / degrees C or less practically required. Thereby, generation | occurrence | production of the curvature, curl, etc. of a laminated body can be suppressed. Although these aromatic tetracarboxylic dianhydride can also be used together with another aromatic tetracarboxylic dianhydride, it is good to use 50 mol% or more of the whole, Preferably it is 70 mol% or more. That is, when selecting tetracarboxylic dianhydride, it is preferable to specifically select the thing suitable for expressing the characteristic required for use, such as the thermal expansion coefficient of a polyimide obtained by superposition | polymerization heating, a thermal decomposition temperature, and a glass transition temperature.

The diamine used as an essential component in the synthesis | combination of the polyimide resin used by this invention is an aromatic diamine represented by following General formula (2).

Here, R has the same meaning as R in general formula (1), but is a C1-C6 hydrocarbon group, Preferably it is an alkyl group of 1-4, or an aryl group of 6. More preferably, they are an ethyl group and n-propyl group or a phenyl group.

The polyimide resin used by this invention can advantageously be obtained by making aromatic tetracarboxylic dianhydride and the diamine containing 10 mol% or more of aromatic diamine represented by the said General formula (2) react.

In this invention, other diamine other than that can be used with the aromatic diamine represented by the said General formula (2) in 90 mol% or less ratio, and it can be set as a copolymer type polyimide by this.

The structural unit represented by General formula (1) is 10-100 mol%, Preferably it is 50-100 mol%, More preferably, it is 70-100 mol%, More preferably, in at least one layer of a polyimide resin layer It is good to contain 90-100 mol%.

The diamines other than the aromatic diamines represented by the general formula (2) are not particularly limited, but for example, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,4-diaminomethylene, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6-xyldine, 4,4'-methylene-2,6-diethylaniline , 2,4-toluenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodi Phenylethane, 3,3'-diaminodiphenylethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy ) Phenyl] propane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4 , 4'-diaminodiphenylether, 3,3-diaminodiphenylether, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1, 4- rain (4-aminophenoxy) benzene, benzidine, 3,3'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 4,4 '-Diamino-p-terphenyl, 3,3'-diamino-p-terphenyl, bis (p-aminocyclohexyl) methane, bis (p-β-amino-t-butylphenyl) ether, bis ( p-β-methyl-δ-aminopentyl) benzene, p-bis (2-methyl-4-aminopentyl) benzene, p-bis (1,1-dimethyl-5-aminopentyl) benzene, 1,5-dia Minonaphthalene, 2,6-diaminonaphthalene, 2,4-bis (β-amino-t-butyl) toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2 , 5-diamine, m-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadia Sol, piperazine, 3,4,4'-triaminophenylether, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl Can be mentioned.

Among them, 4,4'-diaminodiphenyl ether (DAPE), 1,3-bis (4-aminophenoxy) benzene (TPE-R), p-phenyldiamine (p-PDA), 2,2 ' -Dimethyl-4,4'-diaminobiphenyl (m-TB) and the like are preferably used. Moreover, when using these diamine, the preferable use ratio is 0-50 mol% of a total diamine, More preferably, it is the range of 0-30 mol%.

The polyamic acid which becomes a precursor of a polyimide resin can be manufactured by the well-known method of superposing | polymerizing in an organic polar solvent using the aromatic diamine component and aromatic tetracarboxylic dianhydride component shown above in molar ratio of 0.9-1.1. have. That is, after dissolving aromatic diamine in organic solvents, such as N, N- dimethylacetamide and N-methyl- 2-pyrrolidone under nitrogen stream, aromatic tetracarboxylic dianhydride is added and it is 3-4 at room temperature. It is obtained by reacting about time. At this time, the molecular terminal may be sealed with an aromatic monoamine or dicarboxylic anhydride.

When using the aromatic tetracarboxylic dianhydride component containing a naphthalene frame | skeleton, for example, after melt | dissolving an aromatic diamine component in m-cresol under nitrogen stream, the catalyst and aromatic tetracarboxylic dianhydride component are added, 190 It is obtained by heating at about ° C. for about 10 hours, then returning to room temperature, and then further reacting for about 8 hours.

The polyamic acid solution obtained by the above reaction is applied on the metal foil serving as the support or on the adhesive layer formed on the metal foil using an applicator, and imidized by thermal imidization or chemical imidization. The laminated board for wiring boards of this invention is obtained. Thermal imidation is performed by pre-drying for 2 to 60 minutes at the temperature of 150 degrees C or less, and heat-processing about 2 to 30 minutes at the temperature of about 130-360 degreeC normally. Chemical imidation is performed by adding a dehydrating agent and a catalyst to polyamic acid. As metal foil used, copper foil or SUS foil is preferable, The preferable thickness range is 50 micrometers or less, Preferably it is 5-40 micrometers. The copper foil thickness is suitable for formation of a thinner fine pattern, and the range of 8-15 micrometers is preferable from such a viewpoint.

The polyimide resin layer may be a single layer or a multilayer. In the case of a multilayer polyimide resin layer, after repeating the operation of applying and drying a polyamic acid solution, heat treatment is performed to remove the solvent, and heat treatment at high temperature again to imidize the polyimide resin layer having a multilayer structure. Can be formed. At this time, the total thickness of the polyimide resin layer formed is preferably in the range of 3 to 75 µm. In the case of a multilayer, the at least one layer needs to be a polyimide resin layer (hereinafter also referred to as the present polyimide resin layer) containing 10 mol% or more of the structural unit represented by the general formula (1), and the thickness thereof is It is good to set it as 30% or more, preferably 50% or more of the whole polyimide resin layer.

In the case of manufacturing a laminate for wiring boards having metal foil on both sides, after forming a direct or adhesive layer on the polyimide resin layer of the laminate for single-sided wiring board obtained by the above method, the metal foil is heat-compressed. Obtained. Although it does not specifically limit about the hot press temperature at the time of this hot pressing, It is preferable that it is more than the glass transition temperature of the polyimide resin used. In addition, about hot press pressure, although it depends on the kind of press apparatus to be used, it is preferable that it is the range of 1-500 kg / cm <2>. Moreover, the same thing as said metal foil can be used for the preferable metal foil used at this time, The preferable thickness is 50 micrometers or less, More preferably, it is the range of 5-40 micrometers.

The polyimide resin layer constituting the laminate for wiring boards of the present invention has various kinds of aromatic diamines represented by the general formula (2), and other aromatic diamines and aromatic tetracarboxylic acids or acid dianhydrides used therewith. The property can be controlled by the combination. The preferred polyimide resin layer has a linear expansion coefficient of 30 ppm / 占 폚 or less, a storage modulus of 6 GPa or less and a moisture absorption rate of 0.8 wt% or less at 23 占 폚, but the glass transition temperature is 350 占 폚 or more from the viewpoint of heat resistance. The 5% weight loss temperature (Td 5%) in the thermogravimetric analysis is preferably in the range of 500 to 600 ° C, and the humidity expansion coefficient is preferably 10 ppm /% RH or less in both the TD and MD directions. The 5% weight loss temperature is also referred to as the pyrolysis temperature.

EMBODIMENT OF THE INVENTION Hereinafter, although the content of this invention is concretely demonstrated based on an Example, this invention is not limited to the range of these Examples.

The symbol used in the Example etc. is shown below.

ㆍ PMDA: pyromellitic dianhydride

BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride

M-MOB: 2,2'-dimethoxybenzidine

M-EOB: 2,2'-diethoxybenzidine

M-POB: 2,2'-di-n-propyloxybenzidine

M-PHOB: 2,2'-diphenyloxybenzidine

DAPE: 4,4'-diaminodiphenyl ether

M-TB: 2,2'-dimethylbenzidine

TPE-R: 1,3-bis (4-aminophenoxy) benzene

BAPP: 2,2-bis (4-aminophenoxyphenyl) propane

DMAc: N, N-dimethylacetamide

In addition, the measuring method and conditions of various physical properties in an Example are shown below.

[Glass Transition Temperature (Tg), Storage Modulus (E ')]

The dynamic viscoelasticity was measured when the polyimide film (10 mm x 22.6 mm) obtained in each example was heated to 5 ° C / min from 20 ° C to 500 ° C by a dynamic thermomechanical analysis (DMA) apparatus, and the glass transition temperature (tanδ) was measured. maximum value) and 23 ℃, it was obtained the storage modulus (E 'and E _{23' 100)} of 100 ℃.

[Measurement of linear expansion coefficient (CTE)]

A polyimide film having a size of 3 mm x 15 mm was subjected to a tensile test in a temperature range of 30 ° C. to 260 ° C. at a constant heating rate while applying a load of 5.0 g by a thermomechanical analysis (TMA) apparatus. The linear expansion coefficient was calculated | required from the amount of extension of the polyimide film with respect to temperature.

[Measurement of Pyrolysis Temperature (Td 5%)]

The weight change when 10-20 mg of polyimide films were heated up from 30 degreeC to 550 degreeC at constant speed by the thermogravimetric analysis (TG) apparatus was measured, and 5% weight loss temperature (Td 5%) was calculated | required.

[Measurement of Absorption Rate (RMA)]

After drying 4 cm x 20 cm of polyimide films (3 sheets each) at 120 degreeC for 2 hours, they were left to stand in a constant temperature and humidity room of 23 degreeC / 50% RH for 24 hours or more, and the following formula was changed from the weight change before and after that. Obtained by

RMA (%) = [(weight after moisture-weight after drying) / weight after drying] × 100

[Measurement of Humidity Expansion Coefficient (CHE)]

The etching resist layer was formed on the copper foil of 35 cmx35 cm polyimide / copper foil laminated body, and this was formed in the pattern which arrange | positions 12 points of 1 mm diameter at 10 cm intervals on four sides of the square which is one side 30 cm. The copper foil exposed part of the etching resist opening part was etched, and the polyimide film for CHE measurement which has 12 copper foil remaining points was obtained. After drying the film at 120 ° C for 2 hours, the film was allowed to stand for at least 24 hours in a constant temperature and humidity chamber at 23 ° C / 50% RH. Coefficients were obtained.

<Examples>

Synthesis Example 1-18

The polyamic acid used in the Example and the comparative example was synthesize | combined.

Under a stream of nitrogen, the diamines shown in Table 1 were dissolved in 43 g of solvent DMAc while stirring in 100 ml of a detachable flask. Then, tetracarboxylic dianhydride shown in Table 1 was added. Thereafter, the solution was stirred at room temperature for 3 to 4 hours to carry out a polymerization reaction to obtain a yellow to dark brown viscous solution of 18 kinds of polyamic acid (PA) A to R serving as a polyimide precursor. The reduced viscosity (η _sp / C) of each polyamic acid solution was in the range of 3-6. In addition, the weight average molecular weight Mw is shown in Table 1.

Example 1

Before coating the solution of the polyamic acid (PA) A-R obtained by the synthesis examples 1-18, DMAc was added and the viscosity was adjusted to about 250 pois. Then, apply | coated so that the film thickness after drying might be about 15 micrometers on the copper foil of 35 micrometers thickness, respectively, after drying at 50-130 degreeC for 2 to 60 minutes, Furthermore, 130 degreeC, 160 degreeC, 200 degreeC The heat treatment was carried out stepwise for 2 to 30 minutes at 230 ° C, 280 ° C, 320 ° C and 360 ° C, and a polyimide layer was formed on the copper foil to obtain 18 kinds of laminates. The laminated body obtained from the solution of the polyamic acid A obtained by the synthesis example 1 is made into the laminated body A, and it is set as it below. In addition, the laminated body J obtained using the solution of the polyamic acid J obtained by the synthesis example 10 becomes a comparative example. In addition, the laminated body R obtained using the solution of the polyamic acid R obtained by the synthesis example 18 is for evaluating the characteristic of one layer of the polyimide layer of the laminated bodies M1-M3 of a later Example.

About the laminated bodies A-R of Example 1, copper foil was etched away using the ferric chloride aqueous solution, and 18 types of polyimide films were produced, glass transition temperature (Tg), storage modulus (E '), and coefficient of thermal expansion ( CTE), 5% weight loss temperature (Td 5%), moisture absorption rate (RMA) and humidity expansion coefficient (CHE) were measured.

Each measurement result is shown in Table 2

Example 2

The solution of the polyamic acid R prepared in Synthesis Example 18 was uniformly applied to a thickness of 25 μm on a copper foil having a thickness of 18 μm, and then dried at 130 ° C. to remove the solvent. Next, the solution of the polyamic acid E prepared in Synthesis Example 5 was uniformly applied to a thickness of 195 μm so as to be laminated thereon, and dried by heating at 70 ° C. to 130 ° C. to remove the solvent. Furthermore, the solution of the polyamic acid R prepared by the synthesis example 18 on the polyamic acid E layer was apply | coated uniformly to thickness of 37 micrometers, and it heat-dried at 135 degreeC, and the solvent was removed. Then, it heat-treated and imidated at room temperature over 360 degreeC for about 5 hours, and the laminated body M1 in which the insulating resin layer of about 25 micrometers in total thickness which consists of three polyimide-type resin layers was formed on copper foil. The thickness after drying of the polyamic-acid resin layer apply | coated on copper foil is about 2.5 micrometers / about 19 micrometers / about 3.5 micrometers in order of R / E / R.

Examples 3-4

In the same manner as in Example 2, laminates M2 and M3 in which an insulating resin layer having a layer thickness of about 25 μm consisting of three polyimide resin layers were formed on the copper foil were obtained. The kind of polyamic acid solution applied on the copper foil and the thickness after drying, in turn, M2 is R about 2.5 μm / O about 19 μm / R about 3.5 μm, and M3 is R about 2.5 μm / Q about 19 μm / R About 3.5 μm.

Adhesive strength was measured about the laminated bodies M1-M3 obtained in Examples 2-4. Moreover, copper foil was etched away using the ferric chloride aqueous solution, the polyimide film was created, and the coefficient of thermal expansion (CTE) in the three-layer polyimide layer was measured.

Each measurement result is shown in Table 3.

In the laminate for wiring boards of the present invention, the polyimide resin layer serving as the insulating layer is excellent in heat resistance, low moisture absorption, and excellent in dimensional stability, and is capable of suppressing warping due to humidity without involving various problems derived from the adhesive layer. It also has an effect. In addition, the polyimide resin layer of the insulating layer has a feature that there is no anisotropy in the plane because the difference in the coefficient of humidity expansion in the TD direction and the MD direction is small, and can be widely applied to parts in the field of electronic materials. In particular, it is useful for uses, such as a board | substrate for FPC and HDD suspension.

Claims (6)

In a laminate having metal foil on one or both sides of the polyimide resin layer, at least one layer of the polyimide resin layer contains 10 mol% or more of the structural unit represented by the following general formula (1). Substrate laminate. [Formula 1]

In the formula, Ar ₁ is a tetravalent organic group having one or more aromatic rings, and R is a hydrocarbon group having 1 to 6 carbon atoms. The laminate according to claim 1, wherein the polyimide resin layer has a coefficient of linear expansion of 30 ppm / 占 폚 or lower, a storage modulus of 6 GPa or lower, and a moisture absorption rate of 0.8 wt% or lower at 23 占 폚. The laminate according to claim 1, wherein the polyimide resin layer has a 5% weight loss temperature (Td 5%) in a thermal gravimetric analysis in a range of 500 to 600 ° C. The laminate according to claim 2, wherein the polyimide resin layer has a 5% weight loss temperature (Td 5%) in thermal gravimetric analysis in a range of 500 to 600 ° C. The laminate for wiring board according to claim 1, wherein the polyimide resin layer is made of only polyimide resin. A laminate for wiring boards according to claim 1, wherein 50 to 100 mol% of structural units represented by the general formula (1) are contained.