JP2009056771A - Metal/resin composite, circuit substrate and laminated circuit substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal/resin composite which can hardly generate a warping or a debonding in a laminate of a resin layer and a metallic layer, and can be used for an insulating substrate of elements or packages and an insulating radiant plate. <P>SOLUTION: This metal/resin composite is a laminate of a molybdenum metallic layer and a polyimide resin layer. In addition, the metal/resin composite has the coefficient of linear expansion of -5 ppm/°C to +7 ppm/°C and the warping at 350°C of 3% or less. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention has a low linear expansion coefficient as a whole by laminating a specific polyimide resin layer (film) having an equivalent linear expansion coefficient on a Mo (metal molybdenum) layer, which is a low thermal expansion metal, and therefore, at the time of heating. The present invention relates to a metal-resin composite that can be used as a circuit board in which warpage or the like is suppressed, an insulating heat sink, a board of an element that generates a large amount of heat such as a power element, or the like.

Polyimide resins and polyimide films are used for insulating substrates such as printed wiring boards in conventional semiconductor devices (packages), but all polyimide resins and polyimide films are sufficiently satisfactory for environmental durability, especially heat resistance. What can be done, particularly those that have durability against deformation in the plane direction at high temperatures are not known.
In a conventional hybrid integrated circuit (hybrid IC), an element is mounted on a wiring board made of resin or the like, but the linear thermal expansion coefficient of the substrate is considerably higher than the linear thermal expansion coefficient of a silicon chip to be flip-chip mounted. Large (for example, the values are 12 to 13 ppm / ° C. for a glass epoxy substrate, silicon; 3 to 4 ppm / ° C.), and when the flip chip is enlarged and multi-bumped, the stress (stress) on the joint is large. There was a problem that the reliability of became poor.

In order to solve these problems, a hybrid integrated circuit in which the element forming material and a second substrate approximating the coefficient of thermal expansion are joined to the back surface of the wiring board on which the elements are arranged on the front surface, and the elements on the front surface A second substrate that approximates the material for forming the element and the coefficient of thermal expansion thereof is bonded to the back surface of the wiring board on which the wiring board is disposed, and the wiring board and the coefficient of thermal expansion approach the back surface of the second substrate. A hybrid integrated circuit in which a third substrate is bonded (see Patent Document 1) has been proposed, but is not focused on the difference in linear expansion coefficient between the wiring substrate and the second substrate, and is close to the expansion coefficient of the element. By using the second substrate, the reliability of the joint between the element and the wiring substrate / wiring substrate is compensated.
Further, in order to provide a thin and lightweight semiconductor package having excellent connection reliability inside the semiconductor package and less warping deformation, a semiconductor element, a substrate arranged so as to surround the semiconductor element, and one surface side of the substrate A semiconductor package having a wiring layer formed by laminating a wiring connected to the internal connection terminal and an insulating layer on the internal connection terminal side of the semiconductor element, wherein the substrate includes a resin layer, and the semiconductor element A semiconductor package (see Patent Document 2) in which a low thermal expansion metal layer having an average coefficient of thermal expansion of 30 to 200 ° C. surrounding the substrate and having an average thermal expansion coefficient of −5 ppm / ° C. to 10 ppm / ° C. is proposed. The resin layer to be used is a resin film such as epoxy, phenol, BT, polyimide, polyamide, fluororesin, liquid crystal polymer, etc. Examples include prepregs impregnated with woven fabrics and nonwoven fabrics composed of organic fibers such as organic fibers and polyamides. The low thermal expansion metal layer and the resin layer are formed by using temperature and pressure by, for example, a vacuum heating press. It is disclosed that the two are laminated and bonded, and at least the thermal expansion coefficient of the resin layer is not considered.

  Lamination focusing on these expansion coefficients is focused on one of the expansion coefficients, but it is not the one that is laminated with the expansion coefficients of both the (insulating) resin layer and the metal layer almost matched, but expansion between the two. There is no idea of equalizing the coefficients, and it does not focus on warping or peeling as a laminate of a resin layer and a metal layer. In addition, attempts have been made to solve the above problems by using a polyimide film having a low linear expansion coefficient. However, as a conductor metal layer in these conventional techniques, copper having a linear expansion coefficient of about 16 ppm / ° C. Since a metal layer is used, it has been difficult to suppress warpage during high-temperature heating due to a difference between the coefficient of linear expansion of the polyimide film as the insulating material and that of copper.

Japanese Patent No. 2558623 JP, 2004-071698, A In the past, it was thought that Mo was desirable as a low thermal expansion metal layer, but there was a problem in adhesion, and an equivalent linear expansion coefficient was formed on a Mo (metal molybdenum) layer which is a low thermal expansion metal. By laminating a polyimide film mainly composed of polyimide benzoxazole obtained by reacting an aromatic diamine having a benzoxazole structure with an aromatic tetracarboxylic acid anhydride, the linear expansion coefficient is small as a whole. It was difficult to produce a metal resin composite. In addition, the warpage in the temperature range up to 200 ° C. has been a problem in the past, but it has been desired that the laminate having the configuration of Patent 2 can be used even during a process at a high temperature of 350 ° C. This has been difficult with the previous configuration. By laminating a polyimide film having the same linear expansion coefficient on a Mo (metal molybdenum) layer, which is a low thermal expansion metal, a metal resin composite with a low linear expansion coefficient as a whole forms a circuit and maintains insulation. In applications such as, it is desired to reduce the thickness of the polyimide film from the viewpoint of circuit miniaturization, improvement of heat dissipation characteristics, but if it is thin and there is no film thickness fluctuation, Although it was difficult to produce a stable product, it was difficult to produce a polyimide film with a small thickness spot when it became thin.

The present invention provides a laminate of a resin layer and a metal layer by laminating the expansion coefficient of both the (insulating) resin layer and the Mo metal layer so that the expansion coefficients thereof are substantially matched and equalizing the expansion coefficient therebetween. It is intended to provide a metal resin composite that does not easily warp or peel off.
In semiconductor devices that can be miniaturized, high-definition, and high-density, especially semiconductor devices with high power consumption and high heat generation, high production yield and environmental durability, high-density mounting (wiring pitch narrows), Lead-free solder (increase in solder temperature), substrate warpage (curling) due to thermal history such as heat generation due to power consumption, etc., and semiconductor devices that use substrates where lamination between them is difficult to peel off due to thermal history The purpose is to provide an insulating heat sink.
Thermal history in the manufacturing process of the package and the electronic equipment including it, temperature rise and fall when driving the semiconductor, and other components can reduce the occurrence of warpage and deformation due to temperature rise and fall, so it can be connected in the package Reliability and connection reliability with the outside of the package can be improved. When heat is applied locally, the temperature is transmitted and dispersed over a wide area, so the local heat rise can be mitigated.
It has been found that warpage and deformation can be suppressed even during high-temperature heating by a metal resin composite in which a polyimide resin layer having a low linear thermal expansion coefficient and a Mo metal layer having a linear expansion coefficient comparable to that are laminated. The present invention has been reached.

That is, this invention consists of the following structures.
1. A metal resin composite that is a laminate of a Mo metal layer and a polyimide resin layer, and having a linear expansion coefficient of -5 ppm / ° C to +7 ppm / ° C.
2. 1. Warpage at 350 ° C. is 3% or less Metal resin composite.
3. 1. Mo metal layer is directly laminated on polyimide resin layer. ~ 2. Any metal resin composite.
4). 1. The polyimide resin layer is a polyimide film mainly composed of polyimide benzoxazole obtained by reacting an aromatic diamine having a benzoxazole structure with an aromatic tetracarboxylic acid anhydride. ~ 3. Any metal resin composite.
5). 1. Polyimide resin layer thickness is 9 μm or less ~ 4. Any metal resin composite.
6). 1. ~ 5. A circuit board using any metal resin composite.
7). 1. ~ 5. A circuit board in which any metal resin composite is directly electrically bonded to a silicon wafer.
8). 6). ~ 7. A laminated circuit board in which any circuit board is laminated with an inorganic layer having a linear expansion coefficient of +10 ppm / ° C. or less.

A metal resin composite that is a laminate of the Mo metal layer of the present invention and a polyimide resin layer,
Metal resin composites with a linear expansion coefficient of −5 ppm / ° C. to +7 ppm / ° C. are used in high-density mounting (wiring pitch narrows) and lead-free solder (in a small-sized, high-definition, high-density semiconductor device). Thermal history of substrate warpage (curl) due to heat history such as heat generation due to power consumption (lamination of solder temperature) and lamination between both (insulating) resin layer and metal layer (for reinforcement and heat dissipation) It is extremely useful as a circuit-forming substrate and an insulating heat radiating plate that hardly cause peeling.
When the metal resin composite of the present invention is used as a circuit forming substrate or an insulating heat sink in a semiconductor device or the like, thermal history in these manufacturing processes, temperature rise or fall during semiconductor driving, temperature rise or fall due to other components Due to the thermal history due to the above, it is possible to reduce these warping, deformation and delamination, and to improve the connection reliability within the package and the connection reliability with the outside of the package.

In the metal resin composite which is a laminate of the Mo metal layer of the present invention and the polyimide resin layer, and the linear expansion coefficient is −5 ppm / ° C. to +7 ppm / ° C., what is the Mo metal layer? In addition, although it is a layer of Mo alloy containing Mo metal and other metals of an impurity level and Mo alone, it is preferable that the coefficient of linear expansion of at least the metal layer is +4 ppm / ° C. to +7 ppm / ° C.
The method for laminating the Mo metal layer and the polyimide resin layer is not particularly limited, but the polyimide resin layer is cast and imidized by pressure bonding between the Mo metal layer and the polyimide resin layer or the low thermal expansion metal layer. A method of forming a low thermal expansion metal layer on a polyimide film by a dry thin film forming method such as a sputtering method or a vapor deposition method. In this lamination, a method of directly laminating both layers without interposing the other, A method of laminating via an adhesive layer or the like can be mentioned, and a method of laminating both directly without interposing any other between them is preferable.

In the present invention, the linear expansion coefficient is expressed by an average linear expansion coefficient of 30 ° C. to 350 ° C., and the measurement is performed as follows.
“About the polyimide resin layer (film) to be measured and the metal resin composite, the expansion and contraction ratios in the MD direction and the TD direction were measured under the following conditions, and 30 ° C. to 40 ° C., 40 ° C. to 50 ° C., and 10 ° C. The expansion ratio / temperature at intervals was measured, this measurement was performed up to 370 ° C., and the average value of all measured values from 30 ° C. to 350 ° C. was calculated as the coefficient of linear expansion (CTE).
(For the metal layer, in the case of a thin film, the sputtering target or the thin film composition was subjected to fluorescent X-ray analysis, and the measurement was performed with a thin plate having the same composition and a thickness of 0.1 mm within 0.1%. Measure the stretch rate / temperature at intervals of 30 ° C. to 40 ° C., 40 ° C. to 50 ° C., and 10 ° C., perform this measurement up to 370 ° C., and calculate the average value of all measured values from 30 ° C. to 350 ° C. (Calculated as linear expansion coefficient (CTE). In this case, MD and TD are not distinguished.)
Device name: TMA4000S manufactured by MAC Science
Sample length; 10mm
Sample width: 2 mm
Temperature rise start temperature: 25 ° C
Temperature rising end temperature: 400 ° C
Temperature increase rate: 5 ° C / min
Atmosphere: Argon ”

The polyimide resin layer (film) used in the metal resin composite of the present invention is a polyimide resin layer having a linear expansion coefficient of -5 ppm / ° C. to +7 ppm / ° C. from 30 ° C. to 350 ° C. as the metal resin composite. Although not particularly limited, it is preferably a polyimide resin layer or film obtained by reacting aromatic diamines and aromatic tetracarboxylic acids, more preferably an average linear expansion coefficient of 30 ° C to 200 ° C. Is a layer of polyimide resin having −5 ppm / ° C. to 10 ppm / ° C., more preferably −3 ppm / ° C. to 6 ppm / ° C., and particularly preferably 0 ppm / ° C. to 3 ppm / ° C.
The above-mentioned “reaction” is not particularly limited, but preferably a diamine and a tetracarboxylic acid anhydride are subjected to a ring-opening polyaddition reaction in a solvent to obtain a polyamic acid solution. Then, after forming a green film from this polyamic acid solution, it can be produced by dehydration condensation (imidization). The resin layer is a preferred form, but is not limited to this. It may be imidized in the same manner after casting on the expanded metal layer.
In the metal resin composite having a linear expansion coefficient of −5 ppm / ° C. to +7 ppm / ° C. in the present invention, the linear expansion coefficient is more preferably 0 ppm / ° C. to +7 ppm / ° C.
Hereinafter, a film which is one of the polyimide resin layers will be described.
The warpage at 350 ° C. in the present invention is measured by the method described in the measurement item section of the examples, and is preferably 3% or less, more preferably 2% or less, and still more preferably 1.5% or less. belongs to. In order to reduce the warpage, it is necessary to reduce the warpage of the polyimide film alone, but for this purpose, when viewed in the thickness direction of the polyimide film, the linear expansion coefficient in each part matches. It is desirable. If you think about the method of imidization reaction by applying a polyamic acid solution on a support and drying it to obtain a green film and then subjecting the green film to heat treatment, each step is managed under a certain condition. Even if it is possible to suppress variation by simply doing, uniformity in the thickness direction cannot be obtained. The main reason is that the process of applying the polyamic acid solution on the support and drying it cannot be the same on the support side and the opposite side of the support. This is because the solvent does not evaporate on the support side, but only on the opposite side of the support. However, it is difficult to achieve by simply slowing the drying because it affects the process of molecular orientation and imidization that occurs following the drying of the solvent even if the difference between the support side and the opposite side of the support is reduced. Become. By controlling these processes, it is necessary to design a process in which the difference in coefficient of linear expansion in the thickness direction is difficult to occur.
In addition, it is desirable to reduce the thickness of both the polyimide film and the adhesive layer. However, if the thickness is not reduced and the thickness unevenness is small, the occurrence of warpage due to the thickness unevenness and the concentration of stress are also a concern.

In the present invention, the polyimide film used more preferably has a thickness of 9 μm or less, more preferably 6 μm or less, and thickness unevenness of 20% or less, more preferably 10% or less, and even more preferably 5% or less. It is a film. In a tenter type processing unit (conveying device) at the time of manufacturing a thin polyimide film with little thickness unevenness, for example, a polyimide precursor film slit at a narrow width prepared separately from the film to be processed and manufactured at both side ends of the film And / or by superimposing a polyimide film and sticking it together with a pin provided on the pin sheet or holding it with a clip, it can withstand high temperatures up to 500 ° C, such as when imidizing polyamic acid, and has a sufficient reinforcing effect The ultra-thin polyimide film produced as a result can be solved by eliminating the problem of yield loss and poor quality by breaking into a long hole in the longitudinal and width directions of the film. This eliminates the quality problem in the production process and provides an ultra-thin polyimide film with few variability in thickness and excellent dimensional stability. Ultrathin polyimide film is excellent in stability, especially dimensional stability at high temperatures, a less film thicknesses unevenness.
In the present invention, the polyimide film used more preferably is a polyimide film obtained by reacting diamines and tetracarboxylic acids whose aromatic diamines having a benzoxazole structure are in the range of 80 to 100 mol% of the total diamines. For example, as a production method thereof, a polyamic acid solution (A) obtained by reacting an aromatic diamine having a benzoxazole structure with a tetracarboxylic acid, an aromatic diamine having no benzoxazole structure, and The polyamic acid solution (B) obtained by reacting with an aromatic tetracarboxylic acid is a molar ratio of A: B of 80-100: 20-0, preferably A: B of 90-100: 10-0. The mixed solution is applied and cast on a support, dried, and dried to form a self-supporting film (g Nfirumu) was obtained, and the green film was heat-treated in a range of 0.99 ° C. to 500 ° C. The ring closure imidization method include forming a polyimide film, the method is preferably employed.

  In the present invention, specific examples of aromatic diamines having a benzoxazole structure include the following.

Among these, amino (aminophenyl) benzoxazole isomers are preferable from the viewpoint of ease of synthesis. Here, “each isomer” refers to each isomer in which two amino groups of amino (aminophenyl) benzoxazole are determined according to the coordination position (eg, the above “formula 1” to “formula 4”). Each compound described in the above. These diamines may be used alone or in combination of two or more.
In the present invention, apart from the diamine, the following aromatic diamine may be used at less than 20 mol% of the total diamine.
Examples of such diamines include 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, and bis [4- (3-aminophenoxy) phenyl]. Sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine.

  3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide 4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,4'- Diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] methane, 1 , 1-Bi [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] propane, 1 , 2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ]propane.

  1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4- (4-aminophenoxy) phenyl] butane, 1,4-bis [4- (4-aminophenoxy) Phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl] butane, 2- [4- (4-aminophenoxy) Phenyl] -2- [4- (4-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3-methylphenyl] propane, 2- [4- ( 4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphen Le] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane.

  1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) ) Biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- ( 4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,3-bis [4- (4-aminophenoxy) ) Benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3 Aminophenoxy) benzoyl] benzene, 4,4′-bis [4- (3-aminophenoxy) benzoyl] biphenyl, 1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [ 4- (3-Aminophenoxy) phenyl] propane, 3,4'-diaminodiphenyl sulfide.

  2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] methane, 1,1 -Bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, bis [4- (3-aminophenoxy) phenyl] sulfoxide, 4,4 '-Bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino-α) , Α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis 4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3 -Bis [4- (4-amino-6-fluorophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl ] Benzene, 1,3-bis [4- (4-amino-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene.

  3,3′-diamino-4,4′-diphenoxybenzophenone, 4,4′-diamino-5,5′-diphenoxybenzophenone, 3,4′-diamino-4,5′-diphenoxybenzophenone, 3, 3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone, 3,3 '-Diamino-4,4'-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4'-diamino-4,5'-dibiphenoxybenzophenone, 3,3'- Diamino-4-biphenoxybenzophenone, 4,4′-diamino-5-biphenoxybenzophenone, 3,4 -Diamino-4-biphenoxybenzophenone, 3,4'-diamino-5'-biphenoxybenzophenone, 1,3-bis (3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino- 4-phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoxybenzoyl) benzene, 1,4-bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3-amino) -4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4-Amino-5-biphenoxybenzoyl) benzene, 2,6-bis [4- (4-amino-α, α-dimethylbenzyl) pheno Si] benzonitrile and some or all of the hydrogen atoms on the aromatic ring in the aromatic diamine are halogen atoms, alkyl groups having 1 to 3 carbon atoms or alkoxyl groups, cyano groups, or alkyl groups or alkoxyl group hydrogen atoms. Examples thereof include aromatic diamines substituted with a halogenated alkyl group having 1 to 3 carbon atoms partially or wholly substituted with a halogen atom or an alkoxyl group.

  The tetracarboxylic acids used in the present invention are preferably aromatic tetracarboxylic anhydrides. Specific examples of the aromatic tetracarboxylic acid anhydrides include the following. Of these, pyromellitic anhydride of Chemical Formula 4 can be preferably used.

These tetracarboxylic dianhydrides may be used alone or in combination of two or more.
In the present invention, one or two or more non-aromatic tetracarboxylic dianhydrides exemplified below may be used in combination as long as they are less than 10 mol% of the total tetracarboxylic dianhydrides. . Examples of such tetracarboxylic acid anhydrides include butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, and cyclobutanetetracarboxylic acid. Acid dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, cyclohex-1-ene-2,3 5,6-tetracarboxylic dianhydride, 3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3 -(1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride 1-ethylcyclohexane -(1,2), 3,4-tetracarboxylic dianhydride, 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane- 1- (2,3), 3- (2,3) -tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ′, 4′-tetracarboxylic dianhydride.

Bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1 , 3-Dipropylcyclohexane-1- (2,3), 3- (2,3) -tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, bicyclo [2.2.1] Heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and the like. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

  The solvent used when polymerizing diamines and tetracarboxylic acid anhydrides to obtain polyamic acid is not particularly limited as long as it dissolves both the raw material monomer and the polyamic acid to be produced. Organic solvents are preferred, such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphos Examples include hollic amide, ethyl cellosolve acetate, diethylene glycol dimethyl ether, sulfolane, and halogenated phenols. These solvents can be used alone or in combination. The amount of the solvent used may be an amount sufficient to dissolve the monomer as a raw material. As a specific amount used, the weight of the monomer in the solution in which the monomer is dissolved is usually 5 to 40% by weight, The amount is preferably 10 to 30% by weight.

Conventionally known conditions may be applied for the polymerization reaction for obtaining the polyamic acid (hereinafter also simply referred to as “polymerization reaction”). As a specific example, in a temperature range of 0 to 80 ° C., 10 Stirring and / or mixing continuously for minutes to 70 hours. If necessary, the polymerization reaction may be divided or the temperature may be increased or decreased. In this case, the order of adding both monomers is not particularly limited. For example, it is preferable to add aromatic tetracarboxylic acid anhydrides to a solution of aromatic diamines. The weight of the polyamic acid in the polyamic acid solution obtained by the polymerization reaction is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, and the viscosity of the solution is measured with a Brookfield viscometer (25 ° C.). From the viewpoint of the stability of liquid feeding, it is preferably 10 to 2000 Pa · s, and more preferably 100 to 1000 Pa · s.
The reduced viscosity (ηsp / C) of the polyamic acid in the present invention is not particularly limited, but is preferably 2.0 or more, more preferably 3.0 or more, still more preferably 4.0 or more.

Vacuum defoaming during the polymerization reaction is effective for producing a high-quality polyamic acid organic solvent solution. Moreover, you may perform superposition | polymerization by adding a small amount of terminal blockers to aromatic diamines before a polymerization reaction. Examples of the end capping agent include compounds having a carbon-carbon double bond such as maleic anhydride. The amount of maleic anhydride used is preferably 0.001 to 1.0 mol per mol of aromatic diamine.
In order to form a polyimide film from the polyamic acid solution obtained by the polymerization reaction, a green film is obtained by coating the polyamic acid solution on a support and drying, and then subjecting the green film to a heat treatment. A method of imidization reaction may be mentioned.

  The support on which the polyamic acid solution is applied needs only to have smoothness and rigidity sufficient to form the polyamic acid solution into a film, and a drum or belt whose surface is made of metal, plastic, glass, porcelain, etc. And the like. Among them, the surface of the support is preferably a metal, more preferably stainless steel that does not rust and has excellent corrosion resistance. The surface of the support may be plated with metal such as Cr, Ni, or Sn. The surface of the support can be made into a mirror surface as needed, or can be processed into a satin finish. Application of the polyamic acid solution to the support includes, but is not limited to, casting from a slit base, extrusion through an extruder, squeegee coating, reverse coating, die coating, applicator coating, wire bar coating, etc. Conventionally known solution coating means can be appropriately used.

  When the green film is dried to such an extent that self-supporting properties are obtained, a green film having a predetermined range of imidation ratios on the front and back surfaces and the difference between them can be obtained by controlling the amount of residual solvent relative to the total weight after drying. . Specifically, the amount of residual solvent relative to the total weight after drying is preferably 25 to 50% by weight, more preferably 35 to 50% by weight. When the residual solvent amount is lower than 25% by weight, the imidization rate on one side of the green film becomes too high, and it becomes difficult to obtain a green film with a small difference in imidization rate between the front and back surfaces. In addition, the green film tends to become brittle due to a decrease in molecular weight. Moreover, when it exceeds 50 weight%, self-supporting property becomes inadequate and conveyance of a film becomes difficult in many cases.

  As drying conditions for obtaining a green film in which the amount of residual solvent relative to the total weight after drying is within a predetermined range, for example, when N-methylpyrrolidone is used as a solvent, the drying temperature is preferably 70 to 130 ° C., More preferably, it is 75-125 degreeC, More preferably, it is 80-120 degreeC. When the drying temperature is higher than 130 ° C., the molecular weight is lowered and the green film tends to be brittle. In addition, imidization partially proceeds during the production of the green film, and it becomes difficult to obtain desired physical properties during the imidization process. On the other hand, when the temperature is lower than 70 ° C., the drying time becomes long, the molecular weight tends to decrease, and the handling property tends to be poor due to insufficient drying. The drying time is preferably 10 to 90 minutes, more preferably 15 to 80 minutes, although it depends on the drying temperature. When the drying time is longer than 90 minutes, the molecular weight is lowered and the film tends to be brittle. When the drying time is shorter than 10 minutes, the drying property is insufficient and the handling property tends to be poor. Further, in order to improve the drying efficiency or suppress the generation of bubbles at the time of drying, the temperature may be raised stepwise in the range of 70 to 130 ° C. for drying.

A conventionally known drying apparatus that achieves such conditions can be applied, and examples thereof include hot air, hot nitrogen, far infrared rays, and high frequency induction heating.
In the case of performing hot air drying, when the green film is dried to such an extent that self-supporting property is obtained, the range of the imidization ratio on the front and back surfaces of the green film and the difference thereof are set within a predetermined range. It is preferable to control the temperature difference to 10 ° C. or less, preferably 5 ° C. or less, and it is necessary to control the temperature difference by individually controlling the hot air temperature on the upper surface / lower surface.

As a method for imidizing the green film, a conventionally known imidization reaction can be appropriately used. For example, by using a polyamic acid solution that does not contain a ring-closing catalyst or a dehydrating agent, the imidization reaction proceeds by subjecting it to a heat treatment (so-called thermal ring-closing method), or a polycyclic acid solution containing a ring-closing catalyst and a dehydrating agent. In order to obtain a polyimide film in which the difference in surface orientation between the front and back surfaces of the polyimide film is small, a chemical ring closing method can be mentioned in which an imidization reaction is performed by the action of the above ring closing catalyst and dehydrating agent. The thermal ring closure method is preferred.
The maximum heating temperature of the thermal ring closure method is about 100 to 500 ° C, preferably 200 to 480 ° C. When the maximum heating temperature is lower than this range, it is difficult to close the ring sufficiently, and when it is higher than this range, deterioration proceeds and the film tends to become brittle. A more preferable embodiment includes a two-stage heat treatment in which treatment is performed at 150 to 250 ° C. for 3 to 20 minutes and then treatment is performed at 350 to 500 ° C. for 3 to 20 minutes.

In the chemical ring closure method, after the polyamic acid solution is applied to a support, the imidization reaction is partially advanced to form a self-supporting film, and then imidization can be performed completely by heating. In this case, the condition for partially proceeding with the imidization reaction is preferably a heat treatment for 3 to 20 minutes at 100 to 200 ° C., and the condition for allowing the imidization reaction to be completely performed is preferably 200 to 400 ° C. For 3 to 20 minutes.
The timing for adding the ring-closing catalyst to the polyamic acid solution is not particularly limited, and may be added in advance before the polymerization reaction for obtaining the polyamic acid. Specific examples of the ring-closing catalyst include aliphatic tertiary amines such as trimethylamine and triethylamine, and heterocyclic tertiary amines such as isoquinoline, pyridine, and betapicoline. Among them, heterocyclic tertiary amines are mentioned. At least one amine selected from is preferred. Although the usage-amount of a ring-closing catalyst with respect to 1 mol of polyamic acids does not have limitation in particular, Preferably it is 0.5-8 mol.

  The timing of adding the dehydrating agent to the polyamic acid solution is not particularly limited, and may be added in advance before the polymerization reaction for obtaining the polyamic acid. Specific examples of the dehydrating agent include aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride. Among them, acetic anhydride, benzoic anhydride, etc. Acids or mixtures thereof are preferred. Moreover, the usage-amount of the dehydrating agent with respect to 1 mol of polyamic acids is not particularly limited, but is preferably 0.1 to 4 mol. When a dehydrating agent is used, a gelation retarder such as acetylacetone may be used in combination.

Whether it is a thermal cyclization reaction or a chemical cyclization method, the polyimide film precursor (green sheet, film) formed on the support may be peeled off from the support before it is completely imidized. The film may be peeled after imidization.
The thickness of the polyimide film is not particularly limited, but is usually 1 to 100 μm, preferably 1 to 9 μm, and particularly preferably 9 μm or less, more preferably 7 μm or less, and these thin polyimide films. Moreover, the thickness unevenness is a polyimide film of 20% or less, preferably 5% or less, and the warp at a high temperature which is an effect of the present invention by laminating the thin film with a small thickness unevenness and the Mo metal layer. A metal resin composite with a low content can be obtained.
This thickness can be easily controlled by the amount of the polyamic acid solution applied to the support and the concentration of the polyamic acid solution.
The thermal ring closure method is a method in which polyamic acid is imidized by heating. The polyamic acid solution may contain a ring closing catalyst and a dehydrating agent, and the imidization reaction may be promoted by the action of the ring closing catalyst and the dehydrating agent. In this method, after the polyamic acid solution is applied to the support, the imidization reaction is partially advanced to form a film having self-supporting property, and then imidization can be performed completely by heating.
The timing for adding the ring-closing catalyst to the polyamic acid solution is not particularly limited, and may be added in advance before the polymerization reaction for obtaining the polyamic acid. Specific examples of the ring-closing catalyst include aliphatic tertiary amines such as trimethylamine and triethylamine, and heterocyclic tertiary amines such as isoquinoline, pyridine, and betapicoline. Among them, heterocyclic tertiary amines are mentioned. At least one amine selected from is preferred. Although the usage-amount of a ring-closing catalyst with respect to 1 mol of polyamic acids does not have limitation in particular, Preferably it is 0.5-8 mol.

The timing of adding the dehydrating agent to the polyamic acid solution is not particularly limited, and may be added in advance before the polymerization reaction for obtaining the polyamic acid. Specific examples of the dehydrating agent include aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride. Among them, acetic anhydride, benzoic anhydride, etc. Acids or mixtures thereof are preferred. Moreover, the usage-amount of the dehydrating agent with respect to 1 mol of polyamic acids is not particularly limited, but is preferably 0.1 to 4 mol. When a dehydrating agent is used, a gelation retarder such as acetylacetone may be used in combination.
The polyimide film precursor (green sheet, film) formed on the support may be peeled off from the support before complete imidization, or may be peeled off after imidization.

In the polyimide film or resin layer used in the present invention, it is possible to improve the slipperiness of the film or resin layer by adding fine irregularities to the surface of the film or resin layer by adding a lubricant to the polyimide. preferable.
As the lubricant, inorganic or organic fine particles having an average particle diameter of about 0.03 μm to 1 μm can be used. Specific examples include titanium oxide, alumina, silica, calcium carbonate, calcium phosphate, calcium hydrogen phosphate, calcium pyrophosphate. , Magnesium oxide, calcium oxide, clay mineral and the like.
The polyimide film used in the present invention is usually an unstretched film, but may be uniaxially or biaxially stretched. Here, the unstretched film refers to a film obtained without intentionally applying a mechanical external force in the surface expansion direction of the film by tenter stretching, roll stretching, inflation stretching, or the like.

  When creating a circuit board using the metal resin composite of the present invention, it is obtained by forming a circuit of the low thermal expansion metal layer of the metal resin composite of the present invention.

In the present invention, the surface of the polyimide film may be surface-treated before forming the Mo metal layer on the surface of the metal resin composite. For example, the Mo metal layer is laminated on one or both surfaces of the surface-treated polyimide film. In this case, the base metal layer may be formed in advance to form the Mo metal layer, which is the main metal layer. The metal used as the base metal layer is one that strengthens the adhesion to the polyimide film. Although not limited as long as it has properties such as no diffusion, good chemical resistance and heat resistance, chromium, nickel, TiN, and Mo-containing Cu can be given as preferable examples. .
The above-mentioned base metal layer is formed of, for example, at least one selected from the group consisting of metals such as chromium, nickel, TiN, and Mo-containing Cu on one or both surfaces of a surface-treated film, preferably a sputtering method, an ion A base metal layer is formed by vapor deposition by a plating method. In this case, a sputtering method that improves processing stability, simplifies the process, improves the uniformity of the deposited layer, and reduces the occurrence of curling is more preferable.
The film thickness of the base metal layer is preferably in the range of 1 to 50 nm (10 to 500 mm), and more preferably in the range of 2 to 10 nm (20 to 100 mm).

An Mo metal layer can be provided on the base metal layer or directly on the surface of the metal resin composite.
The formation method of these main metal layers should just be a dry film forming method or a wet film forming method, and the film thickness (layer thickness) of this main metal layer has the suitable range of 2 micrometers-50 micrometers.
As described above, the metal resin composite of the present invention can be used extremely effectively as, for example, an FPC (flexible printed wiring board), but the FPC from the metal resin composite of the present invention is High-density mounting (wiring pitch narrows), lead-free solder (solder temperature rise), curling of the substrate due to heat history such as heat generation due to power consumption is suppressed, and the lamination between them is also peeled off by heat history It can be set as the flexible printed wiring board etc. which are hard to produce. In addition, the circuit board produced from the metal resin composite of the present invention is laminated with an inorganic layer having a coefficient of linear expansion (CTE) of +10 ppm / ° C. or less, so that there is no warpage during high temperature heating and high temperature use. As an inorganic layer having a CTE of +10 ppm / ° C. or less, for example, glass such as quartz glass, silicon wafer, silicon chip, Ge substrate, GaAs substrate, ceramic substrate, for example, substrate mainly composed of alumina, glass Low temperature Co-fired Ceramic Substrate
, Beryllia substrate (BeO), steatite substrate (MgO / SiO2), SiC substrate, Mo heat sink, heat sink surface layer with Kovar alloy, Cu-W (W90%) alloy plate, Kovar lead frame, Cu-Ni (Ni 42%) ) Alloy lead frame and the like. Also included are those in which circuit formation, element formation, thin film layer application, etc. are applied to the above-mentioned substrates.
As an adhesive used when laminating a circuit board made from the metal resin composite of the present invention with an inorganic layer having a linear expansion coefficient (CTE) of +10 ppm / ° C. or less, a 5% weight reduction temperature is 400. Adhesives selected from polyimides or polyamideimides at or above ° C are preferred.

  Examples of the present invention will be described below, but the present invention is not limited thereto. In addition, the evaluation method of the physical property in the following examples is as follows.

1. Reduced viscosity of polyamic acid (ηsp / C)
A solution dissolved in N-methyl-2-pyrrolidone so that the polymer concentration was 0.2 g / dl was measured at 25 ° C. with an Ubbelohde type viscosity tube.
(When the solvent used for preparing the polyamic acid solution was N, N-dimethylacetamide, the polymer was dissolved and measured using N, N-dimethylacetamide.)

2. The thickness of the polyimide film The thickness was measured using a micrometer (Millitron 1254D manufactured by Fine Reef).

3. Specimen obtained by cutting a polyimide film to be measured into a strip of 100 mm × 10 mm in the flow direction (MD direction) and the width direction (TD direction), respectively. It was. Using a tensile tester (manufactured by Shimadzu Corporation, Autograph (trade name), model name AG-5000A) under the conditions of a tensile speed of 50 mm / min and a distance between chucks of 40 mm, the tensile modulus of elasticity in each of the MD direction and TD direction, Tensile rupture strength and tensile rupture elongation were measured.

4). Average linear expansion coefficient of polyimide resin layer (film) from 30 ° C to 200 ° C, average linear expansion coefficient of low thermal expansion metal from 30 ° C to 200 ° C, and average linear expansion coefficient of metal resin composite from 30 ° C to 200 ° C Coefficient About the polyimide resin layer (film) to be measured and the metal resin composite, the expansion and contraction ratios in the MD direction and the TD direction were measured under the following conditions, and 30 ° C to 40 ° C, 40 ° C to 50 ° C, ... and 10 ° C. The expansion ratio / temperature at intervals was measured, this measurement was performed up to 250 ° C., and the average value of all measured values from 30 ° C. to 200 ° C. was calculated as the average coefficient of linear expansion (CTE).
The larger value in the MD direction (vertical direction) and the TD direction (width direction) is adopted as the measurement value. When the MD and TD to be measured cannot be distinguished, the measurement is performed in two orthogonal directions, and the value in the larger direction is adopted.
(In addition, about the low thermal expansion metal layer, in the case of the thin film, it measured with the thin plate of thickness 0.1mm thickness of the same composition as the sputter target. 30 to 40 degreeC, 40 to 50 degreeC, ... The stretch ratio / temperature at intervals of 10 ° C. was measured, this measurement was performed up to 250 ° C., and the average value of all measured values from 30 ° C. to 200 ° C. was calculated as the average linear expansion coefficient (CTE). (MD and TD are not distinguished.)

Device name: TMA4000S manufactured by MAC Science
Sample length; 10mm
Sample width: 2 mm
Temperature rise start temperature: 25 ° C
Temperature rising end temperature: 400 ° C
Temperature increase rate: 5 ° C / min
Atmosphere: Argon

5). (5% weight loss temperature)
The film or polymer solution to be measured was sufficiently dried and subjected to thermobalance measurement (TGA) under the following conditions. The temperature at which the weight of the sample was reduced by 5% was defined as the 5% weight reduction temperature.
Device name: TG-DTA2000S manufactured by MAC Science
Pan ： Aluminum pan (non-airtight)
Sample weight: 10mg
Temperature rising start temperature: 30 ° C
Temperature increase rate: 20 ° C / min
Atmosphere: Argon

5. Warpage at 350 ° C (%)
The warpage (%) at 350 ° C. of the metal resin composite means the degree of deformation in the thickness direction with respect to the surface direction of the metal resin composite and film before and after the following predetermined heat treatment. As shown in FIG. 1, a test piece of 50 mm × 50 mm is allowed to stand on a flat surface at room temperature so that the test piece is concave, and the distance from the four corner planes (h1rt, h2rt, h3rt, h4rt: unit The average value of mm) is the original amount of warpage (mm), and after 10 minutes of hot air treatment at 350 ° C., the test piece is left on the plane so as to be concave, and the distance (h1, h2) from the four corner planes , H3, h4: unit mm) is the warpage amount (mm), and the difference from the original warpage amount is the warpage amount at 350 ° C. It is a value expressed as a percentage (%) of the curl amount with respect to the distance (35.36 mm) from each vertex to the center of the test piece.
The sample piece has a total pitch of 2 points in the width direction (1/3 and 2/3 points of the width length) at a 1/5 length pitch with respect to the entire length of the metal-resin composite. The points are sampled and the measured value is the average of 10 points.
However, if there is not enough metal-resin composite to sample 10 points, sample at equal intervals as much as possible. Specifically, it is calculated by the following formula.
Original warpage amount (mm) = (h1rt + h2rt + h3rt + h4rt) / 4
Warpage (mm) = (h1 + h2 + h3 + h4) / 4
Warpage amount at 350 ° C. (mm) = warpage amount−original warpage amount Warpage at 350 ° C. (%) = 100 × (warpage amount at 350 ° C.) / 35.36

6). Separation of the metal layer of the metal resin composite and wrinkle At least 0.3 m of the obtained metal resin composite was sampled and allowed to stand on a horizontal plane, and the peeling and wrinkle of the metal thin film layer were visually observed. The case where peeling and wrinkles were not observed was evaluated as ◎, the case where peeling and wrinkles were slightly observable was evaluated as Δ, and the case where peeling and wrinkles were observed was determined as ×.
7). Thickness unevenness of polyimide film (%)
Thickness unevenness (%) = ((maximum value−minimum value) / average thickness) × 100
About the measurement, it measured using the micrometer (Fine Leuf company make, Millitron 1254D) in the width direction and the longitudinal direction.
For the width direction (TD), the entire width was measured at intervals of 1 cm in the width direction, and the average, maximum value, and minimum value were calculated and calculated using the above formula.
About the longitudinal direction (MD), it measured for 5 m at intervals of 5 cm in the longitudinal direction, and the average, maximum value, and minimum value were calculated and calculated using the above formula.

[Reference Example 1]
(Polyamide acid polymerization-1)
<Polymerization of a polyamic acid composed of a diamine having a benzoxazole structure>
The inside of a reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, and then 500 parts by mass of 5-amino-2- (p-aminophenyl) benzoxazole (DAMBO) was charged. Next, after 8000 parts by mass of N, N-dimethylacetamide was added and completely dissolved, 485 parts by mass of pyromellitic dianhydride (PMDA) was added and stirred at a reaction temperature of 25 ° C. for 48 hours. A viscous polyamic acid solution (A) was obtained. The solution obtained had a ηsp / C of 4.0 dl / g.

[Reference Example 2]
<Polyamide acid polymerization-2>
As tetracarboxylic dianhydride, 398 parts by mass of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 147 parts by mass of paraphenylenediamine (PDA) were added to 4600 parts by mass of N, N-dimethyl. It melt | dissolved in acetamide, it was made to react similarly, keeping temperature at 20 degrees C or less, and the polyamic-acid solution (B) was obtained. The obtained solution had a ηsp / C of 3.0 dl / g.

[Reference Example 3]
<Polyamide acid polymerization-3>
A polyamide obtained by dissolving 545 parts by weight of pyromellitic anhydride and 500 parts by weight of 4,4′diaminodiphenyl ether (ODA) in 8000 parts by weight of N, N-dimethylacetamide and reacting in the same manner while maintaining the temperature at 20 ° C. or lower. An acid solution (C) was obtained. The ηsp / C of the obtained solution was 2.2 and was dl / g.

<Adhesive and its film production-1>
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 368.4 parts by mass of 4,4′-bis (3-aminophenoxy) biphenyl, 59.24 parts by mass of phthalic anhydride, anhydrous 174.5 parts by mass of pyromellitic acid and 2,172 parts by mass of m-cresol were charged, heated to 200 ° C. with stirring, and kept at 200 ° C. for 6 hours. Next, toluene was charged into the reaction solution, the precipitate was filtered off, washed several times with toluene, and then dried at 250 ° C. for 6 hours in a nitrogen atmosphere to obtain 510 parts by mass (yield 90.1). %) Polyimide powder (D). The polyimide powder (D) was kneaded and melted at 380 to 410 ° C. using a twin-screw extruder, extruded and granulated into pellets. The obtained pellets were supplied to a single screw extruder (molding temperature 420 ° C.) having a diameter of 50 mm, passed through a 10 μm leaf disk type filter attached to the front of the T die, extruded from a 1100 mm wide T die, and a thickness of 20 μm. The thermoplastic polyimide film (D) was obtained. The 5% weight loss temperature was 580 ° C.

<Adhesive and its film production-2>
After replacing the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod with nitrogen, 192 parts by mass of trimellitic anhydride, 211 parts by mass of O-tolidine diisocyanate, and 35 parts by mass of 2,4-tolylene diisocyanate were added to the reaction vessel. , 1 part by mass of triethylenediamine and 2500 parts by mass of N-methyl-2-pyrrolidone were added, the temperature was raised to 130 ° C. over 1 hour with stirring, and the reaction was further continued at 130 ° C. for 5 hours, and the logarithmic viscosity was 1.6 dl / g. A polyimide resin solution (E) was obtained. The polyamic acid solution (E) was coated on the non-lubricant surface of polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.) using a comma coater, dried at 120 ° C. for 3 minutes, and then peeled off from the support. Without winding up the polyamic acid film. The polyamic acid film is passed through a pin tenter having three heat treatment zones, the first stage 320 ° C. × 2 minutes, the second stage 320 ° C. × 2 minutes, the third stage 320 ° C. × 2 minutes, and slit to 500 mm width. A polyamideimide film (E) of 20 μm was obtained. The 5% weight loss temperature was 485 ° C.

<Adhesive preparation-3>
In a reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod, 170 parts by mass of 3,4'-diaminodiphenyl ether and 45 parts by mass of 1,3-bis3-aminophenoxybenzene were placed, and after sufficient nitrogen substitution, 1200 parts by mass of N-methyl-2-pyrrolidone dehydrated using molecular sieves was added and completely dissolved.
While cooling this solution to 20 ° C. or lower and stirring, gradually add 268 parts by mass of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 45 parts by mass of 4-phenylethylylphthalic anhydride. added.
32 parts by mass of N-methyl-2-pyrrolidone was added to adjust the polymer concentration to 30% by weight, followed by reaction at room temperature for 24 hours.
The obtained polyamic acid solution (F) was viscous and pale yellow, and ηsp / C was 0.35 dl / g.
Met. The 5% weight loss temperature was 465 ° C.

<Adhesive preparation-4>
In a reaction vessel equipped with a nitrogen introduction tube, a thermometer, a stirring rod, and a glass flask having a capacity of 20 liters, 2,3,3 ′, 4′biphenyltetracarboxylic dianhydride 294.22 parts by mass, triglyme 700 parts by mass Was dissolved while stirring at room temperature, and then 605.30 parts by mass of triglyme and 185 masses of α, ω-bis (3-aminopropyl) polydimethylsiloxane (manufactured by Shin-Etsu Silicon, X-22-161AS, n = 9). Then, the mixture was uniformly dissolved and heated to 185 ° C. in a nitrogen atmosphere for 4 hours while maintaining this temperature. Next, the reaction solution was returned to room temperature and stirred with 62.20 parts by mass of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 23.05 parts by mass of 3,5-diaminobenzoic acid, and triglyme. After adding 509 parts by mass, the reaction temperature was raised to 185 ° C. and the reaction was further continued for 4 hours to produce a polyimidesiloxane solution. This imidosiloxane had a concentration of 40.5% by weight and a solution viscosity of 21 poise. The polyimidesiloxane thus obtained had a yield of 99%, a logarithmic viscosity of 0.23 as a measure of molecular weight, and an imidation ratio of substantially 100%.
6.2 parts by mass of a novolak type epoxy resin (Epicoat 157S-70, manufactured by Yuka Shell Co., Ltd.) was added to 100 parts by mass of this polyimidesiloxane solution, and the mixture was stirred at room temperature (25 ° C.) for 2 hours to uniformly dissolve the polyimide. A siloxane composition solution (G) was obtained. The 5% weight loss temperature was 408 ° C.

<Adhesive and its film production-5>
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 192 parts by mass of trimellitic anhydride, 154 parts by mass of O-tolidine diisocyanate, 3,3 ′, 4,4′-biphenyltetracarboxylic Add 22.5 parts by weight of acid dianhydride, 41 parts by weight of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 1 part by weight of triethylenediamine, and 2500 parts by weight of N-methyl-2-pyrrolidone and stir Then, the temperature was raised to 130 ° C. over 1 hour, and further reacted at 130 ° C. for 5 hours to obtain a polyimide resin solution (H) having a logarithmic viscosity of 1.6 dl / g. The polyamic acid solution (H) was coated on a non-lubricant surface of polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.) using a comma coater, dried at 120 ° C. for 3 minutes, and then peeled off from the support. Without winding up the polyamic acid film. The polyamic acid film is passed through a pin tenter having three heat treatment zones, the first stage 320 ° C. × 2 minutes, the second stage 320 ° C. × 2 minutes, the third stage 320 ° C. × 2 minutes, and slit to 500 mm width. A polyamideimide film (H) of 20 μm was obtained. The 5% weight loss temperature was 504 ° C.

<Adhesive and its film production-6>
After replacing the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod with nitrogen, 190 mass parts and 250 mass parts of trimellitic anhydride (TMA) and oxydianiline diisocyanate were charged in the reaction vessel, respectively. N-methyl-2-pyrrolidone (NMP) was charged to a polymer concentration of 40% and reacted at 120 ° C. for about 1 hour, then heated to 180 ° C. and allowed to react for 5 hours with stirring. Next, while heating was stopped and cooling, N-methyl-2-pyrrolidone was further added and diluted to obtain a polymer solution (I) having a solid content concentration of 20%. After reprecipitation with methanol and drying under reduced pressure, the logarithmic viscosity and the glass transition point were measured and found to be 0.9 dl / g and 290 ° C., respectively. The 5% weight loss temperature was 495 ° C.

<Adhesive resin and film production-7>
30 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 469, Epicoat 1001 manufactured by Yuka Shell Epoxy), 40 parts by mass of cresol novolac type epoxy resin (epoxy equivalent 215, Epiklon N-673 manufactured by Dainippon Ink & Chemicals, Inc.), triazine 30 parts by mass of a structure-containing phenol novolac resin (phenolic hydroxyl group equivalent 120, manufactured by Dainippon Ink & Chemicals, Phenolite KA-7052) was dissolved in 20 parts by mass of ethyl diglycol acetate and 20 parts by mass of solvent naphtha with stirring. 15 parts by mass of terminal epoxidized polybutadiene rubber (manufactured by Nagase Kasei Kogyo Co., Ltd., Denarex R-45EPT), 1.5 parts by mass of pulverized 2-phenyl-4,5-bis (hydroxymethyl) imidazole, and finely pulverized silica 2 Parts by mass, silicon A resin composite solution (J) was prepared by adding 0.5 parts by mass of a foaming agent.
The obtained resin composite solution (J) is applied onto a PET film having a thickness of 38 μm using a roll coater so that the thickness after drying is 20 μm, and then dried at 80 to 120 ° C. for 10 minutes. Thus, an epoxy B stage film (J) of 25 μm was obtained. The 5% weight loss temperature was 345 ° C.

<Polyimide film creation-1>
The polyamic acid solution A obtained in the reference example was coated on a non-slip material surface of a polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.) using a comma coater and dried at 90 ° C. for 60 minutes. The polyamic acid film which became self-supporting after drying was peeled off from the support and cut at both ends to obtain a green film having a thickness of 8.0 μm and a width of 1200 mm. As shown in FIGS. 2 and 3, conditions for pin sheets, brush rolls, press rolls, and support jigs while superimposing a 35 mm wide easy-adhesive narrow long slit film on both side ends of the obtained green film Then, both ends were held with a pin tenter and heat treatment was performed.
The heat treatment settings for the tenter are as follows. The first stage was heated at 180 ° C. for 5 minutes and the heating rate was 4 ° C./second, and the second stage was heated at 460 ° C. for 5 minutes for 2 minutes to proceed the imidization reaction. Then, it is cooled to room temperature in 5 minutes, the part where the easy-adhesive narrow long slit film overlaps on both side edges of the film is cut off with a slitter, rolled up into a roll, and has a long thickness of 5 μm A polyimide film A1 having a thickness variation of 1.5% was obtained.
The easy-adhesive narrow film was prepared in the same manner as described above using a polyamic acid solution A to obtain a 9 μm-thick polyimide film, and 1,3-bis (4-aminophenoxy) benzene and 4 , 4′-oxydiphthalic anhydride and a polyamic acid solution (E), which is an easy-adhesive polyimide precursor obtained, and coated on one surface of the 9 μm-thick polyimide film using a bar coater. And dried at 90 ° C. for 10 minutes to obtain an easily adhesive polyimide film. The ratio of the easy-adhesive layer to the thickness of the 9 μm-thick polyimide film is 0.1 / 1. The obtained easy-adhesive polyimide film was slit to obtain an easy-adhesive narrow (long) film having a width of 35 mm.

<Polyimide film creation-2>
A polyimide film A2 having a thickness of 10 μm and a thickness variation of 4.5% was prepared in the same manner as in polyimide film preparation-1 except that an easy-adhesive narrow (long) film was not used at both ends when imidizing. Obtained

<Polyimide film creation-3>
Except for using the polyamic acid solution (B), a polyimide film B having a thickness of 8.5 μm and a thickness variation of 8.5% was obtained in the same manner as in polyimide film preparation-2.

<Polyimide film creation-4>
Except for using the polyamic acid solution (C), a polyimide film C having a thickness of 9.5% and a thickness of 9.5% was obtained in the same manner as in polyimide film preparation-2.

<Preparation of Mo laminated composite>
The long film A1 obtained above was put into a continuous sputtering apparatus, evacuated and then rolled up, and gas was discharged from the film. Thereafter, the surface of the polyimide film was treated with oxygen glow discharge. Thereafter, the film was taken out from the surface treatment apparatus, and a Mo underlayer thin film layer having a thickness of 20 nm was formed on one surface of the film by a DC magnetron sputtering method using argon gas with Mo metal as a target. The degree of vacuum at the time of forming the thin film layer is 3 × 10 −3 Torr.
As the composition of the Mo electroless plating bath, ammonium molybdate is used, Mo is 2 mol / liter, organic carboxylic acid derivative is 12 mol / liter, and electroless plating bath stabilizer such as ammonium chloride is 0.3 mol / liter. In addition, pH was adjusted to 7 using ammonia as a pH adjuster. It was immersed for 10 minutes under the condition of a bath temperature of 90 ° C. to obtain a Mo laminated composite A1-Mo having a Mo layer of 0.8 μm.
Similarly, using the film A2, the film B, and the film C, respective Mo laminated composites, A2-Mo, B-Mo, and C-Mo were prepared.
Each of these Mo laminated composites, A1-Mo, A2-Mo, B-Mo, and C-Mo, was collected from a 50 mm × 50 mm test piece and treated with hot air at 350 ° C. for 10 minutes. Two points in the width direction (1/3 and 2/3 points of the width length) at a 1/5 length pitch with respect to the entire length of the Mo laminated composite which is a metal resin composite, are used as the center points of the test piece. A total of 10 points were sampled, and the measured value was the average of 10 points). Table 1 shows the physical properties of each film and the warpage of each metal resin composite at 350 ° C.

<Creation of Cu laminated composite>
The long film A1 obtained above (with a width of 250 mm) was put in a sputtering apparatus, evacuated and then rolled back, and gas was discharged from the film. Thereafter, the surface of the polyimide film was treated with oxygen glow discharge. Thereafter, the NiCr base thin film layer having a thickness of 15 nm was formed on one surface of the film by a DC magnetron sputtering method using an argon gas with a NiCr alloy as a target. The degree of vacuum at the time of forming the thin film layer is 3 × 10 −3 Torr. Then, a copper thin film layer having a thickness of 250 nm was immediately formed by DC magnetron sputtering using argon gas with copper as a target. The composition of the target NiCr alloy was Ni 80 wt% and Cr 20 wt% purity 3N. The target Cu had a purity of 4N. Each target has a rectangular shape with a width of 12 cm in the film feeding direction and a width of 27 cm in the film feeding direction. Four rectangular targets are installed in the film feeding direction.
Since the distance between the targets used for Cu is separated, the NiCr sputtered atoms and the Cu atoms do not reach the film after being mixed in a vacuum, and the underlying NiCr thin film and Cu thin film Each thin film is formed without intermingling to form a two-layer thin film.
The sputtering device is a roll-to-roll system, and surface treatment, NiCr layer preparation, and Cu layer preparation are sequentially performed while the film is moved from the roll to the unwinding chamber, the sputtering chamber, the preliminary chamber, and the winding chamber. And then wound on a roll.
Each chamber is roughly partitioned by a slit. In the sputtering chamber, the film is in contact with the chill roll, and is cooled by the temperature of the chill roll (−5 ° C.), but does not use one NiCr target, one target near the unwinding side, and then from the two Cu targets. A thin film is formed by the metal particles.
The plating was performed on one side by bringing the electrode into contact with the sputtering metal layer using a roll-to-roll electroplating apparatus. As a result, ACL of CCL as a metallized polyimide film was obtained. Used in Comparative Example 1.

<Attaching Mo-CL to the substrate>
The inorganic substrates used are as follows.
Inorganic substrate A: Si wafer back-grinded to a thickness of 150 μm, polished by stress relief finish and diced to 30 mm × 30 mm square Inorganic substrate B: Glass; 7059
Inorganic substrate C: Alumina substrate Inorganic substrate D: Mo plate

<Example 1>
Two sheets of thermoplastic polyimide film (D) are placed on inorganic substrate A, and film Mo laminated composite (A1-Mo) is further placed on substrate A in a direction in which the polyimide surface faces the inorganic substrate A surface. After placing and positioning, pressing was performed at 280 ° C. for 10 minutes. The pressure at this time was 10 MPa. After the pressing, heat treatment was further performed at 400 ° C. for 30 minutes in a muffle furnace with N2 flow to obtain a test multilayer substrate as a laminate.

<Example 2>
A test multilayer substrate as a laminate was obtained in the same manner as in Example 1 except that the polyamideimide film (E) was used and the press temperature was 350 ° C.

<Example 3>
The polyimide composition solution (F) is applied on the polyimide surface of the film Mo laminated composite (A1-Mo) using a roll coater so that the thickness after drying is 25 μm, and then dried at 100 ° C. for 1 hour. Then, the film with an adhesive layer was obtained by baking at 300 ° C. for 1 hour in a muffle furnace. Two films with an adhesive layer are placed on the inorganic substrate A with the adhesive surface on the polyimide facing the inorganic substrate A surface, positioned, vacuum pressed at 350 ° C, and used as a laminate. A multilayer substrate was obtained.

<Example 4>
After applying the polyimide composition solution (G) on the surface of the film (A1-Mo) using a roll coater so that the thickness after drying is 25 μm, the adhesive layer is dried at 90 ° C. for 5 minutes. A sticky film was obtained. Two films with an adhesive layer are placed on the inorganic substrate A with the adhesive surface on the polyimide facing the inorganic substrate A surface, positioned, vacuum pressed at 120 ° C., and then hot air dryer Heat treatment was performed at 80 ° C. for 80 minutes and 120 ° C. for 120 minutes to obtain a multilayer test substrate as a laminate.

<Example 5>
A multilayer test substrate as a laminate was obtained in the same manner as in Example 2 except that the polyamideimide film (H) was used and the pressing temperature was 380 ° C.

<Example 6>
The polyimide composition solution (I) is applied on the surface of the film Mo laminated composite (A1-Mo) using a bar coater so that the thickness after drying is 25 μm, and then dried at 90 ° C. for 1 hour. Thus, a film with an adhesive layer was obtained. Two films with an adhesive layer were placed on the inorganic substrate A in such a direction that the adhesive surface on the polyimide faced the inorganic substrate A surface, positioned, and pressed at 280 ° C. for 10 minutes. The pressure at this time was 10 MPa. After the pressing, heat treatment was further performed at 400 ° C. for 30 minutes in a muffle furnace with N2 flow to obtain a test multilayer substrate as a laminate.

<Example 7>
A test multilayer substrate of Example 7 was obtained in the same manner as Example 1 except that the substrate B was used.

<Example 8>
A test multilayer substrate of Example 7 was obtained in the same manner as in Example 1 except that the substrate C was used.

<Example 9>
A test multilayer substrate of Example 7 was obtained in the same manner as in Example 1 except that the substrate D was used.

<Example 10>
A test multilayer substrate of Example 7 was obtained in the same manner as in Example 1 except that the film Mo laminated composite A2 was used.

<Example 11>
A test multilayer substrate of Example 7 was obtained in the same manner as in Example 1 except that the film Mo laminated composite B was used.

<Comparative Example 1>
Comparative Example 1 Multi-layer for test in the same manner as in Example 1 except that C1-ACL of CCL, which is a metallized polyimide film prepared in the preparation of Cu laminated composite, was used instead of A1-Mo in Example 1. A substrate was obtained.

<Comparative example 2>
A multilayer substrate for testing Comparative Example 2 was obtained in the same manner as in Example 2 except that the Mo laminated composite C-Mo made of polyimide film C was used.

<Comparative Example 3>
A multilayer substrate for test of Comparative Example 3 was obtained in the same manner as in Example 1 except that the epoxy B stage film (I) was used as an adhesive and the pressing temperature was 250 ° C.

Samples of 30 mm × 30 mm were taken from the test multilayer substrates obtained in these examples and comparative examples, and were placed on a horizontal plane to be a laminate of an inorganic substrate and a Mo metal layer / polyimide resin (film) layer. Visually observe peeling and wrinkles in the adhesive layer between ◎, where peeling and wrinkles are hardly observed ◎, peeling and wrinkles can be observed slightly ○, peeling and wrinkles can be observed a lot Judged as x. The results are shown in Table 2.

A metal resin composite that is a laminate of a Mo metal layer and a polyimide resin layer according to the present invention and has a linear expansion coefficient of −5 ppm / ° C. to +7 ppm / ° C. By laminating a specific polyimide resin layer (film) having an equivalent linear expansion coefficient on the Mo layer, which is a low thermal expansion metal, the linear expansion coefficient is small as a whole, and as a laminate of a resin layer and a metal layer Warpage and delamination are unlikely to occur, reducing thermal history in the manufacturing process of elements and packages and electronic devices including them, temperature rise and fall when driving semiconductors, and other components causing warpage and deformation due to temperature rise and fall From this, it is possible to improve the connection reliability within the package and the connection reliability with the outside of the package, such as flexible printed wiring boards, multilayer boards, TAB, COF, COG, etc. Board large element of a thermal, industrial significance can be used as such low CTE of the wiring material is extremely large.
When glass or the like is used as a substrate, this smoothness and flatness are used, so it is advantageous for fine circuit formation even in the production by the build-up. By using photosensitive glass, the via diameter can be reduced. Since it is possible, a fine pattern can be formed even in the glass portion.
When a transparent substrate such as glass is used, it is also effective as a support substrate for light, electrical transmission substrate creation, light emission, and light receiving element alone, which also has the effect of transmitting optical signals.
Because the substrate is extremely gas-barrier, it is also ideal for applications that require gas-barrier properties, and because it is bonded to glass with high gas-barrier properties, the gas permeation of the bonded part is reduced and extremely high reliability. It is a very meaningful product in the industry.

Schematic diagram showing the measurement method of curl degree of metal resin composite

The outline of the pin sheet | seat which provided the stand in the width direction outer side of the pin which contacts the film in the pin tenter type film processing machine which is one of the preferable aspects of this invention is shown. (A) is a front view, (b) is a side view.

The outline of the pin insertion part of the film in the pin tenter type film processing machine which is one of the preferable aspects of this invention is shown.

Explanation of symbols

In FIG.
1, 2, 3, 4 indicate the corners of each plane in the plane of the metal resin composite.

2 and 3,
1: Brush roll 2: Pin 3: Pin base 4: Base 5: Support jig 6: Pressing roll 7: Precursor film

Claims (8)

  A metal resin composite that is a laminate of a Mo metal layer and a polyimide resin layer, and having a linear expansion coefficient of -5 ppm / ° C to +7 ppm / ° C.   The metal resin composite according to claim 1, wherein a warpage (%) at 350 ° C. is 3% or less.   The metal resin composite according to claim 1, wherein the Mo metal layer is directly laminated on the polyimide resin layer.   The polyimide resin layer is a polyimide film mainly composed of polyimide benzoxazole obtained by reacting an aromatic diamine having a benzoxazole structure with an aromatic tetracarboxylic acid anhydride. The metal resin composite in any one of -3. The metal resin composite according to claim 1, wherein the polyimide resin layer has a thickness of 9 μm or less. A circuit board using the metal resin composite according to claim 1. A circuit board in which the metal resin composite according to claim 1 is directly electrically bonded to a silicon wafer. A laminated circuit board obtained by laminating the circuit board according to claim 6 with an inorganic layer having a linear expansion coefficient of +10 ppm / ° C. or less.

Images