JP2012097150A - Polyesterimide resin composition, and prepreg impregnated therewith, laminate and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyesterimide resin composition that is good in drillability, can give laminates little in warpage even at high temperature, and has good impregnating ability and high glass transition temperature.SOLUTION: The polyesterimide resin composition includes a polyesterimide resin comprising structural units represented by formula (1) and formula (2), wherein the content of the structural units of formula (1) is 50 to 95 mol%, and an inorganic filler [in formula (1), Arand Arare each aryl, which may be identical or different; Rand Rare each independently H, alkyl or alkoxy; X is -NH-C(=O)- or -C(=O)-NH-; n is 1 or 2; when n is 2, two X present in formula (1) may be identical or different, in formula (2), Arand Arare the same as Arand Arin formula (1); Aris a divalent group having an aromatic ring or aliphatic ring].

Description

  The present invention relates to a polyesterimide resin composition, a prepreg impregnated with the polyesterimide resin composition, a laminate, and a semiconductor device.

  2. Description of the Related Art In recent years, with the enhancement of functionality of electronic devices, electronic components have been densely integrated and mounted with high density, and the demand for miniaturization and thinning of semiconductor packages and the like has further increased. However, a conventional semiconductor package substrate or printed wiring board using an epoxy resin or a cyanate resin has a problem that a defect such as a connection failure occurs due to warpage caused by thinning. Such warpage of the substrate is improved by increasing the amount of filler added, but there is a problem that the drillability of the substrate is lowered.

  On the other hand, a polyimide resin is a resin excellent in heat resistance, chemical resistance, electrical insulation, and mechanical properties, and its application to a substrate material is being studied. However, even when a polyimide resin is used, there is a problem that the substrate warps as described above. Furthermore, the polyimide resin is generally difficult to dissolve in a solvent, and it is difficult to mold the substrate using a resin varnish. There was a problem. For this reason, improvement of the solvent solubility of a polyimide resin and reduction of a thermal expansion coefficient are examined.

  For example, JP 2009-235111 A (Patent Document 1) discloses a polyimide resin containing a diamine residue having a fluorene skeleton and a diamine residue having a biphenyl skeleton or a phenylene skeleton. Japanese Patent Application Laid-Open No. 2010-53336 (Patent Document 2) discloses a polyimide resin containing a diamine residue having a tolidinesulfonic acid skeleton. Although these polyimide resins show good solubility in solvents, their thermal expansion coefficients have not been sufficiently low.

  Japanese Unexamined Patent Application Publication No. 2009-286854 (Patent Document 3) discloses a polyesterimide resin having an ester bond and a precursor thereof. Although this polyesterimide resin has a low coefficient of thermal expansion, its solubility in a solvent is low, and it has been difficult to form a substrate using a resin varnish. For this reason, when using the said polyesterimide resin as a board | substrate material, it was necessary to use the polyester amide acid which is a polyesterimide resin precursor excellent in solvent solubility as a resin for board | substrate materials. However, in general, when a substrate is produced using polyamic acid, there is a problem that a dehydrating imidization reaction occurs during press molding, and voids and molding defects are caused by generated water.

  For this reason, in order to use a polyimide resin as a substrate material, a polyimide resin that is soluble in a solvent and has a low thermal expansion coefficient after imidization is required.

JP 2009-235311 A JP 2010-53336 A JP 2009-286854 A

  The present invention has been made in view of the above-mentioned problems of the prior art, contains a polyesterimide resin soluble in a solvent, exhibits good impregnation properties before curing, and has a high glass transition temperature and a high viscosity after curing. Polyesterimide resin composition having a low coefficient of linear thermal expansion, further having good drillability, and capable of obtaining a laminate with less warpage even at high temperatures, and a polyesterimide resin composition using the same An object is to provide a prepreg, a laminate, and a semiconductor device.

  As a result of intensive studies to achieve the above object, the present inventors have obtained an acid anhydride ester residue containing a biphenyl skeleton having an aryl group as a substituent and an aromatic diamine residue containing an amide bond. The polyesterimide resin containing the structural unit at a predetermined ratio exhibits good solubility in a solvent, and by using such a polyesterimide resin, a polyesterimide resin composition having the above characteristics can be obtained. The inventors have found that a laminate having the above-mentioned characteristics can be obtained by using the polyesterimide resin composition, and the present invention has been completed.

  That is, the polyesterimide resin composition of the present invention has the following formula (1):

(In the formula (1), Ar ¹ and Ar ² represent an aryl group, which may be the same or different, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group and an alkoxy group. Any one of the groups, X represents —NH—C (═O) — or —C (═O) —NH—, n is 1 or 2, and when n is 2, the formula ( 1) The two Xs present in them may be the same or different.)
A structural unit A represented by:
Following formula (2):

(In the formula (2), Ar ¹ and Ar ² are the same as the Ar ¹ and Ar ² in the formula (1), Ar ³ represents a divalent group having an aromatic ring or aliphatic ring .)
And a polyesterimide resin having a content of the structural unit A of 50 to 95 mol%, and an inorganic filler.

In the polyesterimide resin composition of the present invention, Ar ¹ and Ar ² in the formula (1) and the formula (2) are each independently a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group. Preferably there is.

Ar ³ in the formula (2) is represented by the following formulas (I) to (VIII):

(K in the formula (I) is an integer of 0 to 5, and R ³ and R ⁴ in the formula (III) are each independently a hydrogen atom, an alkyl group, a halogenated alkyl group or a hydroxyl group. R ⁵ and R ⁶ in formula (IV) each independently represent a hydrogen atom or an alkyl group, and R ⁷ and R ^{8 in} formula (V) each independently represent a hydrogen atom, a halogen atom or an alkyl group Represents any one of a group and a hydroxyl group, and R ⁹ and R ^{10 in} formula (VIII) each independently represent any one of a hydrogen atom, a halogen atom, an alkyl group, and a hydroxyl group.)
It is preferable that it is either of the bivalent groups represented by these.

  The prepreg of the present invention is characterized in that the base material is impregnated with the polyesterimide resin composition of the present invention, and the laminate of the present invention is a layer formed by subjecting this prepreg to heat treatment. It is characterized by providing. In addition, a semiconductor device of the present invention includes the laminated plate of the present invention and a semiconductor element disposed on the laminated plate.

  In addition, the polyesterimide resin containing the structural unit A represented by the said Formula (1) and the structural unit B represented by the said Formula (2) shows favorable solvent solubility, Resin containing this polyesterimide resin The reason why the composition exhibits good impregnation before curing is not necessarily clear, but the present inventors infer as follows. That is, since the polyesterimide resin according to the present invention has a bulky side chain substituent (aryl group) in the biphenyl skeleton, the intermolecular interaction is relaxed, and it has an amide bond. It is presumed that the solvation effect is manifested, shows good solubility in the solvent, and shows good impregnation in the substrate.

  The reason why the polyesterimide resin composition of the present invention exhibits a high glass transition temperature and a low linear thermal expansion coefficient after curing is not necessarily clear, but the present inventors speculate as follows. That is, since the polyesterimide resin according to the present invention has a rigid skeleton such as a biphenyl skeleton or an amide bond in which an ester group is bonded to the para position, the polyesterimide resin exhibits high orientation and has a self-planar structure due to the biphenyl skeleton. It is assumed that a dense molecular packing is formed due to the stacking property. It is surmised that such high orientation and molecular packing formation make it difficult for molecules to be deformed by heat, exhibiting a high glass transition temperature and a low linear thermal expansion coefficient.

  According to the present invention, there is provided a polyesterimide resin composition containing a polyesterimide resin soluble in a solvent, exhibiting good impregnation before curing, and having a high glass transition temperature and a low linear thermal expansion coefficient after curing. In addition, it is possible to obtain a polyesterimide resin composition that has a better drill workability and can obtain a laminated board with less warping even at high temperatures, and a prepreg, laminated board, and semiconductor device using the same. Become.

It is a graph which shows the infrared absorption (FT-IR) spectrum of the polyesterimide resin obtained by the synthesis example 1.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

<Polyesterimide resin composition>
First, the polyesterimide resin composition of the present invention will be described. The polyesterimide resin composition of the present invention comprises a polyester containing a structural unit A composed of an acid anhydride ester residue containing a specific biphenyl skeleton and a specific aromatic diamine residue containing an amide bond in a predetermined ratio. It contains an imide resin and an inorganic filler.

(Polyesterimide resin)
The polyesterimide resin used in the present invention has the following formula (1):

And a structural unit A represented by the following formula (2):

The structural unit B represented by these is contained. The structural unit A and the structural unit B have different structures.

Ar ¹ and Ar ² in the formula (1) represent an aryl group, which may be the same or different, and Ar ¹ and Ar ² in the formula (2) are It is the same as Ar ¹ and Ar ^{2 in} (1). In the structural units A and B, the presence of an aryl group as a substituent of the biphenyl skeleton alleviates the intermolecular interaction of the polyesterimide resin and improves the solvent solubility. Such an aryl group is preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group. Examples of the substituted phenyl group include alkylphenyl groups such as a methylphenyl group and an ethylphenyl group. In addition, examples of the substituted naphthyl group include alkyl naphthyl groups such as a methyl naphthyl group and an ethyl naphthyl group.

  X in the formula (1) represents —NH—C (═O) — or —C (═O) —NH—, and n is 1 or 2. When n is 2, two Xs in the formula (1) may be the same (for example, an aromatic diamine residue containing an amide bond is represented by the following formula (a)). Different ones (for example, an aromatic diamine residue containing an amide bond represented by the following formula (b)) may be used.

(R in the formulas (a) and (b) is each independently R ¹ or R ² in the formula (1).)
By the presence of an amide bond in the structural unit A, the linear thermal expansion coefficient after curing of the polyesterimide resin composition is reduced, and the dimensional stability is improved. As a result, by using such a polyesterimide resin composition, it is possible to obtain a laminated board with less warpage.

R ¹ and R ² in the formula (1) each independently represent any of a hydrogen atom, an alkyl group, and an alkoxy group. Examples of the alkyl group include a methyl group and an ethyl group, and examples of the alkoxy group include a methoxy group and an ethoxy group. Among these, from the viewpoint that the linear thermal expansion coefficient after curing of the polyesterimide resin composition is further reduced and the warpage of the laminate is reduced, R ¹ and R ² are preferably a hydrogen atom or an alkyl group, A hydrogen atom and a methyl group are more preferable, and a hydrogen atom is particularly preferable.

Ar ³ in the formula (2) represents a divalent group having an aromatic ring or an aliphatic ring. However, the following formula (c):

^{(R 1, R} 2, X and n in the formula (c), the formula (1) the same meanings as ^{R 1, R} 2, X and n in.)
It is different from the divalent group represented by As Ar ³ in the formula (2), from the viewpoint that the intermolecular interaction of the polyesterimide resin is relaxed and the solvent solubility is improved, the following formulas (I) to (VIII):

A divalent group represented by any of the above is preferable, a flexible bending structure is partially introduced into the polyesterimide resin, the intermolecular interaction of the polyesterimide resin is moderately relaxed, and moderate solvent solubility is exhibited. From the viewpoint that, what is represented by the formula (I) is more preferable, from the viewpoint that the linear thermal expansion coefficient after curing of the polyesterimide resin composition is further reduced, and the warpage of the laminate is reduced. Those represented by the formulas (III), (IV) and (VIII) are more preferred.

K in the said formula (I) is an integer of 0-5, and it is preferable that it is an integer of 0-2. R ³ and R ⁴ in the formula (III) each independently represent any one of a hydrogen atom, an alkyl group, a halogenated alkyl group and a hydroxyl group, and among them, a hydrogen atom, a methyl group, a halogenated methyl group, A hydroxyl group is preferred. R ⁵ and R ⁶ in the formula (IV) each independently represent a hydrogen atom or an alkyl group, and among them, a hydrogen atom and a methyl group are preferable. R ⁷ and R ⁸ in the formula (V) each independently represent any one of a hydrogen atom, a halogen atom, an alkyl group and a hydroxyl group, and among them, a hydrogen atom is preferable. R ⁹ and R ¹⁰ in the formula (VIII) each independently represent a hydrogen atom or an alkyl group, and among them, a hydrogen atom and a methyl group are preferable.

  In the polyesterimide resin according to the present invention, the content of the structural unit A represented by the formula (1) is 50 to 95 mol% with respect to the entire structural unit (100 mol%) of the polyesterimide resin. The content rate of the structural unit B represented by the said Formula (2) is 5-50 mol%. When the content of the structural unit A is less than 50 mol% (or when the content of the structural unit B exceeds 50 mol%), the linear thermal expansion coefficient of the cured product of the polyesterimide resin is increased, If the content of the structural unit A exceeds 95 mol% (or if the content of the structural unit B is less than 5 mol%), it is difficult to uniformly dissolve the polyesterimide resin in the solvent. Further, from the viewpoint that the solvent solubility of the polyesterimide resin becomes higher and the linear thermal expansion coefficient becomes lower, the content of the structural unit A is preferably 60 to 90 mol%, The content is preferably 10 to 40 mol%.

  Such a polyesterimide resin exhibits good solubility in a solvent. Examples of the solvent include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), 1,3-dimethylimidazolidinone, and tetramethylurea. Amide solvents, phosphorus-containing solvents such as hexamethylphosphoric amide and hexamethylphosphine triamide, sulfur-containing solvents such as dimethyl sulfoxide (DMSO) and sulfolane, γ-butyrolactone (GBL), γ-valerolactone, γ- Lactone solvents such as caprolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-ki Phenolic solvents such as Renol, 3,5-xylenol, 3-chlorophenol, 4-chlorophenol, ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, acetophenone, Examples thereof include ketone solvents such as cyclohexanone and methyl isobutyl ketone. The polyesterimide resin also has good heat meltability.

  Such a cured product of polyesterimide resin has a high glass transition temperature (Tg) and a low coefficient of linear thermal expansion (CTE). Tg is preferably 250 ° C. or higher, and more preferably 260 ° C. or higher. Moreover, as CTE, 20 ppm / K or less is preferable and 17 ppm / K or less is more preferable. In addition, although there is no restriction | limiting in particular as an upper limit of Tg, Usually, it is 400 degrees C or less. The lower limit of CTE is not particularly limited, but is usually 3 ppm / K or more.

(Production method of polyesterimide resin)
The polyesterimide resin according to the present invention includes, for example, the following formula (3):

An acid anhydride ester represented by the following formula (4):

An aromatic diamine containing an amide bond represented by the following (hereinafter referred to as “diamine A”) and the following formula (5):
^{_{H 2 N-Ar 3 -NH 2}} (5)
Other diamines represented by (hereinafter referred to as “diamine B”),
Is reacted to give the following formula (6):

It is produced by forming a structural unit of a polyesterimide precursor (polyamic acid) soluble in a solvent represented by the formula, and subjecting the carboxyl group and amide group of this polyesterimide precursor to a ring-closing reaction by dehydration treatment. Can do.

Ar ¹ and Ar ² in the formula (3) and (6) in the above formula (1) have the same meanings as Ar ¹ and Ar ² of, ^{R 1, R} 2 in the formula (4), X and n has the same meaning as ^{R 1, R} 2, X and n in the formula (1), Ar ³ in the formula (5) has the same meaning as Ar ³ in the formula (2), of the present invention Y in the formula (6) which is a structural unit of a polyesterimide precursor (polyamic acid) soluble in a solvent is a residue of the diamine A (that is, a divalent group represented by the formula (c)) or It represents the residue of the diamine B (that is, Ar ³ in the formula (5)).

As the diamine B, Ar ³ in the formula (5) is any one of the formulas (I) to (VIII) from the viewpoint that the intermolecular interaction of the polyesterimide resin is relaxed and the solvent solubility is improved. A diamine which is a divalent group represented by the formula is preferable, a flexible bending structure is partially introduced into the polyesterimide resin, the intermolecular interaction of the polyesterimide resin is moderately relaxed, and moderate solvent solubility is exhibited. From the viewpoint, diamine in which Ar ³ in the formula (5) is a divalent group represented by the formula (I) is more preferable, and the linear thermal expansion coefficient after curing of the polyesterimide resin composition is more From the viewpoint that the warpage of the laminated sheet is reduced, Ar ³ in the formula (5) is a divalent group represented by the formula (III), (IV), or (VIII). Is more preferable.

  When the acid anhydride ester and the diamine component (the diamine A and the diamine B) are reacted, the reaction temperature is not particularly limited, and the reaction can be performed at room temperature. This reaction is preferably performed in a solvent. The solvent used here is not particularly limited, but N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), 1,3-dimethylimidazo Amide solvents such as lysinone and tetramethylurea, phosphorus-containing solvents such as hexamethylphosphoric amide and hexamethylphosphine triamide, sulfur-containing solvents such as dimethyl sulfoxide (DMSO) and sulfolane, γ-butyrolactone (GBL) Lactone solvents such as γ-valerolactone and γ-caprolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4- Xylenol, 2,5-xylenol, 2,6 Phenol solvents such as xylenol, 3,4-xylenol, 3,5-xylenol, 3-chlorophenol, 4-chlorophenol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, etc. Examples include ether solvents, ketone solvents such as acetophenone, cyclohexanone, and methyl isobutyl ketone. Among them, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), γ-butyrolactone ( GBL) and the like are preferable.

  The mixing ratio of the acid anhydride ester and the diamine component is not particularly limited. For example, the acid anhydride ester component: diamine component (molar ratio) = 2.0: 1.0 to 1.0: 2.0 is preferable. 1.2: 1.0 to 1.0: 1.2 is more preferable.

  Moreover, in reaction of the said acid anhydride ester and the said diamine component, the mixing molar ratio (diamine A: diamine B) of diamine A and diamine B is 50: 50-95: 5. Thereby, the polyesterimide resin whose content rate of the structural unit A represented by the said Formula (1) is 50-95 mol% can be manufactured. Furthermore, the content ratio of the structural unit A can be adjusted by adjusting the mixing molar ratio. For example, by setting the diamine A: diamine B = 60: 40 to 90:10, the structural unit A A polyesterimide resin having a content of 60 to 90 mol% can be produced.

  By subjecting the polyesterimide precursor thus obtained to a dehydration treatment, the carboxyl group and the amide group undergo a ring-closing reaction, and the polyesterimide resin according to the present invention can be obtained. Examples of the dehydration treatment include a heat dehydration treatment at 150 to 180 ° C. and a chemical dehydration treatment using a dehydrating agent such as acetic anhydride / pyridine. Further, such a ring closure reaction is preferably performed in a solvent. Although there is no restriction | limiting in particular as a solvent used here, What was used in reaction of the said acid anhydride ester and the said diamine component can be used as it is. In order to azeotropically distill off water, which is a by-product during the imidation reaction, toluene, xylene, etc. can be added to these solvents, and for the purpose of further promoting the imidization reaction, pyridine, triethylamine, γ -A base such as picoline can also be added.

(Inorganic filler)
The polyesterimide resin composition of the present invention contains an inorganic filler. By containing an inorganic filler, the fluidity of the polyesterimide resin composition can be controlled, the linear thermal expansion coefficient after curing of the polyesterimide resin composition can be reduced, or the flame retardancy can be improved. It becomes possible.

  Such inorganic fillers are not particularly limited, but include, for example, silicates such as talc, calcined clay, unfired clay, mica and glass, oxides such as titanium oxide, alumina, silica and fused silica, calcium carbonate , Carbonates such as magnesium carbonate and hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite, zinc borate, and metaborate Borates such as barium oxide, aluminum borate, calcium borate and sodium borate, nitrides such as aluminum nitride, boron nitride, silicon nitride and carbon nitride, titanates such as strontium titanate and barium titanate Known inorganic fillers can be used, and among them, it is preferable to use fused silica. Arbitrariness. Moreover, there is no restriction | limiting in particular as a shape of an inorganic filler, Although spherical shape, plate shape, needle shape, fiber shape, etc. are mentioned, Among these, spherical shape is preferable.

  Although there is no restriction | limiting in particular as an average particle diameter of the said inorganic filler, 0.01-5.0 micrometers is preferable and 0.1-2.0 micrometers is especially preferable. When the average particle size of the inorganic filler is less than the lower limit, the varnish has a high viscosity, which may affect the workability during prepreg production. Moreover, when the said upper limit is exceeded, the phenomenon that an inorganic filler settles in a varnish may occur.

  In the polyesterimide resin composition of the present invention, the content of the inorganic filler is preferably 30 to 80% by mass and more preferably 50 to 70% by mass with respect to the total amount of the polyesterimide resin and the inorganic filler. When the content of the inorganic filler is less than the lower limit, the thermal expansion coefficient of the laminate produced using the polyesterimide resin composition tends to increase. On the other hand, when the upper limit is exceeded, drilling of the laminate is performed. Tend to decrease.

(Coupling agent)
In the polyesterimide resin composition of the present invention, a coupling agent is preferably contained. By including the coupling agent, the wettability of the interface between the polyesterimide resin and the inorganic filler can be improved, and thereby the polyesterimide resin and the inorganic filler can be added to the fiber substrate and the like. It is possible to fix uniformly and to improve heat resistance, particularly solder heat resistance after moisture absorption. Such a coupling agent is not particularly limited, but silane coupling agents such as epoxy silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, and cationic silane coupling agents, and titanate coupling agents. It is preferable to use one or more coupling agents selected from silicone oil type coupling agents. As content of such a coupling agent, 0.05-5 mass parts is preferable with respect to 100 mass parts of total amounts of a polyesterimide resin and an inorganic filler, and 0.1-3 mass parts is more preferable. If the content of the coupling agent is less than the lower limit, it tends to be difficult to uniformly disperse the inorganic filler in the polyesterimide resin. On the other hand, if the content exceeds the upper limit, the physical properties of the polyesterimide resin composition. Tend to decrease.

(solvent)
The polyesterimide resin composition of the present invention may contain a solvent. As such a solvent, those in which the polyesterimide resin exhibits good solubility, for example, the solvents exemplified above are preferable. Although there is no restriction | limiting in particular as content of a solvent, From the viewpoint that the impregnation property of a polyesterimide resin composition improves, the quantity from which resin solid content concentration will be 5-30 mass% (more preferably 10-25 mass%) Is preferred.

(Polyesterimide resin composition)
The polyesterimide resin composition of this invention can be manufactured by mixing the said polyesterimide resin, an inorganic filler, and a coupling agent as needed. Moreover, a resin varnish can be obtained by mixing a solvent. As a method for producing such a resin varnish, a reaction liquid containing the polyesterimide resin and a solvent used in the synthesis thereof, an inorganic filler, a coupling agent as required, and other semiconductor package substrates and prints are used. A method for obtaining a resin varnish by mixing a known additive in a resin composition used for a wiring board, or after isolating the polyesterimide resin from a reaction solution, and then obtaining the polyesterimide resin and an inorganic filler Any procedures and methods that can be usually applied, such as a method of obtaining a resin varnish by mixing the above-mentioned components such as a coupling agent, if necessary, with a suitable solvent, can be employed. In addition, as a method for mixing the inorganic filler and the coupling agent, the inorganic filler and the coupling agent are mixed in advance by dry mixing or wet mixing and the inorganic filler is treated with the coupling agent, and then the polyesterimide resin is mixed. The method of mixing with the remaining resin varnish components such as, the method of mixing the inorganic filler and the coupling agent into the remaining resin varnish components separately, and the treatment with the coupling agent dispersed in a solvent in advance or untreated inorganic Any generally applicable procedure and method, such as a method of mixing the filler with the remaining resin varnish components, can be employed.

  Such a polyesterimide resin composition exhibits good impregnation before curing, and exhibits a high glass transition temperature (Tg) and a low coefficient of linear thermal expansion (CTE) after curing. Tg is preferably 250 ° C. or higher, and more preferably 260 ° C. or higher. Moreover, as CTE, 20 ppm / K or less is preferable and 5 ppm / K or less is more preferable. In addition, although there is no restriction | limiting in particular as an upper limit of Tg, Usually, it is 400 degrees C or less. The lower limit of CTE is not particularly limited, but is usually 0.5 ppm / K or more.

  Since the polyesterimide resin composition of the present invention has a low coefficient of linear thermal expansion after curing, it becomes possible to form a laminated board with less warpage. Moreover, since it is not necessary to increase content of an inorganic filler when the linear thermal expansion coefficient after hardening is low, the drill workability of a laminated board also decreases.

  Next, the prepreg, laminate and semiconductor device of the present invention will be described.

<Prepreg>
The prepreg of the present invention is obtained by impregnating a base material with the polyesterimide resin composition of the present invention and drying it as necessary. As the base material used in the prepreg of the present invention, glass fiber base materials such as glass woven fabric, glass nonwoven fabric, and glass paper; organic materials such as paper (pulp), aramid fiber, polyester fiber, aromatic polyester fiber, and fluororesin fiber Examples thereof include woven fabrics and nonwoven fabrics composed of fibers; woven fabrics, nonwoven fabrics, mats and the like composed of metal fibers, carbon fibers, mineral fibers, and the like. These base materials may be used individually by 1 type, or may use 2 or more types together.

  Although there is no restriction | limiting in particular as a method to impregnate the polyesterimide resin composition of this invention in such a base material, For example, the polyesterimide resin composition (resin varnish) containing the said solvent is prepared, and a base material is prepared for this. Examples include a dipping method; a method in which a polyesterimide resin composition or the resin varnish is applied or applied to a substrate using a coater; and a method in which the polyesterimide resin composition or the resin varnish is sprayed onto the substrate by spraying. Among these, the method of immersing the base material in the resin varnish is preferable in that the polyesterimide resin composition can be more uniformly impregnated.

  Moreover, when a prepreg is produced, if necessary, a drying treatment is performed to prevent volatile components such as a solvent from volatilely evaporating when producing a laminated board of the present invention described later (when performing a heat treatment). be able to. There is no restriction | limiting in particular as such drying conditions, Temperature, a pressure (for example, pressure reduction), etc. can be selected suitably.

<Laminated plate>
The laminated board of this invention is equipped with the layer formed by heat-processing to the prepreg of this invention. The prepreg may be a single sheet or two or more sheets. When manufacturing such a laminated board, heat treatment may be applied to a prepreg in which one or a plurality of layers are laminated before forming (laminating) other layers to be described later. After other layers are formed (laminated) thereon, it is preferable to collectively heat-treat them. Thereby, the adhesiveness of the interface between the laminated prepregs becomes high, and there is a tendency that physical property deterioration due to delamination does not easily occur. Examples of the heat treatment include heating and pressing.

  Although there is no restriction | limiting in particular as temperature of such heat processing, 220-300 degreeC is preferable. Since the polyesterimide resin according to the present invention has a good heat melting property, by performing heat treatment at such a temperature, the polyesterimide resin melts and diffuses in the base material, and the polyesterimide resin composition becomes the base material. It becomes possible to form a layer that exists more uniformly therein. Moreover, when performing a pressurization process, although there is no restriction | limiting in particular as a pressure to pressurize, 1-4 MPa is preferable. Moreover, when manufacturing the laminated board of this invention, it does not interfere at all to use apparatuses, such as a vacuum press well-known to those skilled in the art, as needed.

  Although there is no restriction | limiting in particular as another layer in the laminated board of this invention, For example, metal foil, such as copper foil, copper alloy foil, aluminum foil, aluminum alloy foil, is mentioned. A laminated board provided with such a metal foil can be used as a printed wiring board by performing circuit processing.

  Since the polyesterimide resin composition of the present invention has a low coefficient of linear thermal expansion after curing, the laminate of the present invention formed using the polyesterimide resin composition is less warped even at high temperatures. Moreover, since it is not necessary to increase content of an inorganic filler when the linear thermal expansion coefficient after hardening of a resin composition is low, in the laminated board of this invention, it is less likely that drill workability falls.

<Semiconductor device>
The semiconductor device of the present invention includes the laminate of the present invention and a semiconductor substrate disposed on the laminate. The semiconductor element is not particularly limited, and a known semiconductor element such as a TEG chip can be used. Since such a semiconductor device includes a stacked body with less warping, poor connection hardly occurs and connection reliability is excellent.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. Abbreviations and chemical formulas of acid anhydrides and diamines used for the synthesis of polyimide resins are shown below.
(1) Acid anhydride / OPPBP-TME: 3,3′-diphenyl-4,4′-biphenol-bis (trimellitate anhydrite) (manufactured by Honshu Chemical Industry Co., Ltd.)

OTBP-TME: 3,3'-di (4-tolyl) -4,4'-biphenol-bis (trimellitic anhydrite)

・ＯＮＢＰ−ＴＭＥ：３，３’−ジ（１−ナフチル）−４，４’−ビフェノール−ビス（トリメリテートアンハイドライト）

ONBP-TME: 3,3′-di (1-naphthyl) -4,4′-biphenol-bis (trimellitic anhydrite)

PMDA: pyromellitic anhydride (Wako Pure Chemical Industries, Ltd. (reagent))

BPDA: 4,4'-biphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd. (reagent))

・ DSDA: 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd.)

BP-TME: 4,4'-biphenol-bis (trimellitate anhydrite) (Honshu Chemical Industry Co., Ltd.)

(2) Diamine / DABAN: 4,4′-diaminobenzanilide (manufactured by Nippon Pure Chemicals Co., Ltd.)

MDABAN: 4,4'-diamino-2'-methylbenzanilide (manufactured by Nippon Pure Chemicals Co., Ltd.)

・ MODABAN: 4,4'-diamino-2'-methoxybenzanilide (manufactured by Nippon Pure Chemicals Co., Ltd.)

APTP: N, N'-bis (4-aminophenyl) terephthalamide (manufactured by Nippon Pure Chemicals Co., Ltd.)

ODA: 4,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd. (reagent))

DMB: 4,4'-diamino-3,3'-dimethylbiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd. (reagent))

DDS: 3,3'-diaminodiphenylsulfone (manufactured by Tokyo Chemical Industry Co., Ltd. (reagent))

-DADMTSN: 3,7-diamino-2,8-dimethyldibenzothiophene sulfone (manufactured by Tokyo Chemical Industry Co., Ltd. (reagent))

ABP: 1,4-bis (4-aminobenzoyl) piperazine (manufactured by Nippon Pure Chemicals Co., Ltd.)

・ BAFL: 9,9-bis (4-aminophenyl) fluorene (manufactured by JFE Chemical Co., Ltd.)

APB: 1,3-bis (3-aminophenoxy) benzene (Mitsui Chemical Fine Co., Ltd.)

  In addition, about OTBP-TME and ONBP-TME, it synthesize | combined with the following method, About other acid anhydrides and diamine, it acquired from each manufacturer.

(Synthesis method of OTBP-TME)
(1) Synthesis of 3,3′-di (4-tolyl) -4,4′-biphenol (OTBP) To a 1 L four-necked flask equipped with a thermometer, a condenser, and a stirrer, 2- (4-tolyl) ) -4-Bromophenol 84.20 g (0.320 mol), 5 mol / L sodium hydroxide aqueous solution 280 ml, 5% palladium / carbon catalyst 0.70 g, dioxane 280 ml were charged, and the temperature was raised to about 90 ° C. with stirring. Warm up. While maintaining the temperature of the solution at around 90 ° C., an aqueous solution of 26.26 g (0.160 mol) of hydroxylamine sulfate dissolved in 70 ml of water was added dropwise to the solution over 3 hours. After completion of dropping, the reaction was continued while heating at 90 ° C. for 1 hour. The resulting reaction solution was filtered to separate the palladium / carbon catalyst. The filtrate was neutralized to about pH 4 with hydrochloric acid, 150 ml of chloroform was added, and the mixture was extracted at 50 ° C. to separate the chloroform layer. The separated chloroform solution was washed twice with 150 ml of pure water, then desolvated and distilled under reduced pressure to remove the monophenol component. Thereafter, the residue was recrystallized using isopropyl ether / acetone and vacuum-dried to obtain 38.90 g of white crystalline powder. The yield was 66.0%. The crystals obtained by FT-IR and ¹ H-NMR were analyzed, and the target structure (OTBP) was confirmed.

(2) Synthesis of OTBP-TME In a 1 L four-necked flask equipped with a thermometer, a reflux condenser, and a dropping funnel, 50.54 g (0.240 mol) of trimellitic anhydride chloride, 180 g of methyl isobutyl ketone, 80 g of acetone Was dissolved while cooling to 0 to 5 ° C. On the other hand, 36.65 g (0.100 mol) of OTBP synthesized in (1), 17.42 g (0.300 mol) of pyridine, and 30.0 g of methyl isobutyl ketone were mixed and dissolved at room temperature. This solution was dropped into the four-necked flask using the dropping funnel over 2 hours with stirring while maintaining the temperature at 0 to 5 ° C. to carry out the reaction. After completion of dropping, the mixture was further stirred at a temperature of 0 to 5 ° C. for 1 hour, and then reacted at 70 ° C. with stirring for 6 hours. After completion of the reaction, aqueous hydrochloric acid and water were added and stirred, and then the aqueous layer was separated. After adding water to the obtained oil layer and stirring, the operation of separating the aqueous layer (washing with water) was repeated four times to remove the by-product pyridine hydrochloride. Since the target product is ring-opened during washing with water to form a tetracarboxylic acid, 40.84 g (0.400 mol) of acetic anhydride is added to the oil layer after washing with water, and the ring is closed at a temperature of 80 to 90 ° C. for 20 hours. It was. The obtained solution was cooled to room temperature, and the precipitated crystals were filtered to obtain 51.46 g of white crystals. The yield was 72.0%. The crystals obtained by FT-IR and ¹ H-NMR were analyzed, and the target structure (OTBP-TME) was confirmed.

(Synthesis method of ONBP-TME)
(1) Synthesis of 3,3′-di (1-naphthyl) -4,4′-biphenol (ONBP) 2- (1-naphthyl) -4 instead of 2- (4-tolyl) -4-bromophenol -White crystalline powder 50.61g was obtained by the method similar to the said OTBP synthesis method except having used 95.73g (0.320 mol) of bromophenol. The yield was 72.1%. The crystals obtained by FT-IR and ¹ H-NMR were analyzed and confirmed to have the target structure (ONBP).

(2) Synthesis of ONBP-TME White crystals 55. were synthesized by the same method as the synthesis method of OTBP-TME except that 43.85 g (0.100 mol) of ONBP synthesized in (1) was used instead of OTBP. 31 g was obtained. The yield was 70.3%. The crystals obtained by FT-IR and ¹ H-NMR were analyzed, and the target structure (ONBP-TME) was confirmed.

(Synthesis Example 1)
In a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 7.95 g (0.035 mol) of DABAN and 3.01 (0.015 mol) of ODA are used as diamine components. Then, 40.0 g of N-methyl-2-pyrrolidone was added and stirred at 60 ° C. to dissolve. After the diamine component was uniformly dissolved, the resulting solution was cooled to room temperature, and 34.30 g (0.050 mol) of powdered OPPBP-TME was added to the flask in several portions as the acid anhydride component. The mixture was reacted at room temperature for 48 hours to obtain a polyesterimide precursor solution.

  A Dean-Stark tube is attached to the flask, and 10.2 g of toluene is added as an azeotropic solvent to the polyesterimide precursor solution in the flask, and a reflux reaction is performed at 185 ° C. in a nitrogen stream to remove generated water out of the system. The reflux reaction was continued for 6 hours. After the reaction, the reaction solution was cooled to room temperature, diluted appropriately with NMP, dropped into 1 L of methanol to perform reprecipitation, and the resin powder was isolated by suction filtration. The obtained resin powder was further washed with 1 L of methanol, filtered and air dried, and further vacuum dried at 120 ° C. for 24 hours to obtain 40.6 g of purified resin powder. The yield was 90%.

The purified resin powder obtained by FT-IR and ¹ H-NMR was analyzed, and a polyesterimide resin having the target structure (the molar ratio of the structural unit A to the structural unit B was A: B = 7: 3). It was confirmed that The infrared absorption (FT-IR) spectrum of this polyesterimide resin was measured by a KBr transmission method using a Fourier transform infrared spectrophotometer (“FTIR-8900” manufactured by Shimadzu Corporation). The result is shown in FIG.

(Synthesis Example 2)
A polyesterimide resin having the desired structure (with the structural unit A and the same) as in Synthesis Example 1 except that 9.65 g (0.040 mol) of MDBAN and 2.00 g (0.010 mol) of ODA were used as the diamine component. 40.3 g of the structural unit B was synthesized (containing the molar ratio A: B = 8: 2). The yield was 88%.

(Synthesis Example 3)
A polyesterimide resin having the desired structure (with the structural unit A and the same as in Synthesis Example 1) except that 11.58 g (0.045 mol) of MODABAN and 1.00 g (0.005 mol) of ODA were used as the diamine component. 40.2 g of the above structural unit B was synthesized (containing the molar ratio A: B = 9: 1). The yield was 86%.

(Synthesis Example 4)
A polyesterimide resin having the desired structure (with the structural unit A and the above) was used in the same manner as in Synthesis Example 1 except that 10.39 g (0.030 mol) of APTP and 6.97 g (0.020 mol) of ODA were used as the diamine component. 47.4 g) was synthesized (containing the structural unit B in a molar ratio A: B = 6: 4). The yield was 92%.

(Synthesis Example 5)
A polyesterimide resin having the desired structure (with the structural unit A and the above) was used in the same manner as in Synthesis Example 1 except that 7.95 g (0.035 mol) of DABAN and 3.72 g (0.015 mol) of DMB were used as the diamine component. 41.7 g) was synthesized (containing the structural unit B at a molar ratio A: B = 7: 3). The yield was 91%.

(Synthesis Example 6)
A polyesterimide resin having the desired structure (with the structural unit A and the above) was used in the same manner as in Synthesis Example 1 except that 9.09 g (0.040 mol) of DABAN and 2.48 g (0.010 mol) of DDS were used as the diamine component. 41.2 g of the above structural unit B was synthesized (containing the molar ratio A: B = 8: 2). The yield was 90%.

(Synthesis Example 7)
A polyesterimide resin having the desired structure (with the structural unit A and the above) was used in the same manner as in Synthesis Example 1 except that 6.82 g (0.030 mol) of DABAN and 5.49 g (0.020 mol) of DADMTSN were used as the diamine component. 40.0 g of a compound containing the structural unit B in a molar ratio A: B = 6: 4) was synthesized. The yield was 86%.

(Synthesis Example 8)
A polyesterimide resin having the desired structure (with the structural unit A and the same) as in Synthesis Example 1 except that 13.86 g (0.040 mol) of APTP and 3.24 g (0.010 mol) of ABP were used as the diamine component. 45.2 g) was synthesized (containing the structural unit B at a molar ratio A: B = 8: 2). The yield was 89%.

(Synthesis Example 9)
The same as Synthesis Example 1 except that 35.73 g (0.050 mol) of OTBP-TME was used as the acid anhydride component, and 10.23 g (0.045 mol) of DABAN and 1.74 g (0.005 mol) of BAFL were used as the diamine component. 41.8 g of a polyesterimide resin having a target structure (containing the structural unit A and the structural unit B in a molar ratio A: B = 9: 1) was synthesized. The yield was 88%.

(Synthesis Example 10)
The same as Synthesis Example 1 except that 39.33 g (0.050 mol) of ONBP-TME was used as the acid anhydride component, and 10.23 g (0.045 mol) of DABAN and 1.74 g (0.005 mol) of BAFL were used as the diamine component. Then, 43.5 g of a polyesterimide resin having the target structure (containing the structural unit A and the structural unit B at a molar ratio A: B = 9: 1) was synthesized. The yield was 85%.

(Comparative Synthesis Example 1)
A polyimide resin was synthesized in the same manner as in Synthesis Example 1 except that PMDA 10.91 g (0.050 mol) was used as the acid anhydride component, and the reaction product was precipitated during the reflux reaction at 185 ° C. The reflux reaction was continued for 6 hours. After the reaction, the reaction solution and the precipitate were put into 1 L of methanol for reprecipitation, and the resin powder was isolated by suction filtration. The obtained resin powder was further washed with 1 L of methanol, filtered and air-dried, and further vacuum-dried at 120 ° C. for 24 hours to obtain 19.9 g of a purified resin (polyimide resin) powder. The yield was 92%.

(Comparative Synthesis Example 2)
A polyimide resin was synthesized in the same manner as in Synthesis Example 1 except that 14.71 g (0.050 mol) of BPDA was used as the acid anhydride component, and the reaction product was precipitated during the reflux reaction at 185 ° C. The reflux reaction was continued for 6 hours. After the reaction, 23.2 g of purified resin (polyimide resin) powder was obtained in the same manner as in Comparative Synthesis Example 1. The yield was 91%.

(Comparative Synthesis Example 3)
A polyimide resin was synthesized in the same manner as in Synthesis Example 1 except that 17.90 g (0.050 mol) of DSDA was used as the acid anhydride component, and the reactant was precipitated during the reflux reaction at 185 ° C. The reflux reaction was continued for 6 hours. After the reaction, 23.5 g of purified resin (polyimide resin) powder was obtained in the same manner as in Comparative Synthesis Example 1. The yield was 82%.

(Comparative Synthesis Example 4)
The same as Synthesis Example 1 except that 26.72 g (0.050 mol) of BP-TME was used as the acid anhydride component, and 6.70 g (0.025 mol) of DABAN and 5.01 (0.025 mol) of ODA were used as the diamine component. When the polyimide resin was synthesized, a reaction product precipitated during the reflux reaction at 185 ° C., but the reflux reaction was continued for 6 hours. After the reaction, 36.0 g of purified resin (polyimide resin) powder was obtained in the same manner as in Comparative Synthesis Example 1. The yield was 94%.

(Comparative Synthesis Example 5)
A polyimide resin was synthesized in the same manner as in Synthesis Example 1 except that 14.71 g (0.050 mol) of BPDA was used as the acid anhydride component and ODA10.01 (0.050 mol) was used as the diamine component. During the reflux reaction, a reaction product was precipitated, but the reflux reaction was continued for 6 hours. After the reaction, 21.8 g of purified resin (polyimide resin) powder was obtained in the same manner as in Comparative Synthesis Example 1. The yield was 89%.

(Comparative Synthesis Example 6)
26.5 g of purified resin (polyimide resin) powder was obtained in the same manner as in Synthesis Example 1 except that 17.90 g (0.050 mol) of DSDA was used as the acid anhydride component and 14.62 (0.050 mol) of APB was used as the diamine component. Synthesized. The yield was 82%.

(Comparative Synthesis Example 7)
A polyimide resin was synthesized in the same manner as in Synthesis Example 1 except that BP-TME26.72 g (0.050 mol) was used as the acid anhydride component and BAFL 17.42 (0.050 mol) was used as the diamine component. While the reaction product was precipitated during the reflux reaction at 185 ° C., the reflux reaction was continued for 6 hours. After the reaction, 38.7 g of purified resin (polyimide resin) powder was obtained in the same manner as in Comparative Synthesis Example 1. The yield was 88%.

(Comparative Synthesis Example 8)
A polyimide resin was synthesized in the same manner as in Synthesis Example 1 except that DABAN 11.36 (0.050 mol) was used as the diamine component. After completion of the reflux reaction at 185 ° C., the reaction solution was cooled to room temperature. Gelation occurred. The gelled product was put into 1 L of methanol and the precipitated solid was pulverized with a mixer, and the resin powder was isolated by suction filtration. The obtained resin powder was further washed with 1 L of methanol, filtered and air-dried, and further vacuum-dried at 120 ° C. for 24 hours to obtain 41.0 g of purified resin (polyimide resin) powder. The yield was 90%.

(Comparative Synthesis Example 9)
40.8 g of purified resin (polyimide resin) powder was synthesized in the same manner as in Synthesis Example 1 except that DABAN 3.41 (0.015 mol) and BAFL 12.20 (0.035 mol) were used as the diamine component. The yield was 84%.

(Comparative Synthesis Example 10)
A purified resin (polyimide resin) powder 42.3 g was synthesized in the same manner as in Synthesis Example 1 except that BAFL 17.42 (0.050 mol) was used as the diamine component. The yield was 82%.

  The characteristic evaluation method of the obtained polyimide resin is shown below.

(1) Solvent solubility N-methyl-2-pyrrolidone (NMP) was added to the polyimide resin so that the resin concentration was 10% by mass, and the mixture was mixed by stirring while heating at 60 ° C. to prepare a solution. The solution was cooled to room temperature, and allowed to stand at room temperature for 24 hours. The state of the solution was visually observed, and the solubility of the resin was evaluated in the following three stages. The results are shown in Table 1.
A: Precipitates and gelled products are not seen and excellent in uniform and transparent solubility.
B: Slight deposits and gelled products are seen, and slightly insoluble.
C: A clear precipitate or gelled product is seen and the solubility is poor.

(2) Reduced viscosity NMP was added to the polyimide resin to prepare a solution having a resin concentration of 0.5 mass%, and the reduced viscosity at 30 ° C of this solution was measured using an Ubbelohde viscometer. The results are shown in Table 1.

(3) Glass transition temperature NMP was added to the polyimide resin to prepare a varnish having a resin concentration of 10% by mass. This varnish is cast on a glass substrate, dried in air at 80 ° C. for 2 hours, further dried in a nitrogen oven at 200 ° C. for 2 hours, and then the polyimide film is peeled off from the substrate to remove residual stress. Then, heat treatment was performed in vacuum at 250 ° C. for 1 hour to obtain a polyimide film having a thickness of 30 μm.

  For this polyimide film, using a viscoelastic spectrometer (“DMS6100” manufactured by SII Nanotechnology Co., Ltd.), a dynamic viscoelasticity measurement is performed under the conditions of a frequency of 0.1 Hz and a heating rate of 5 ° C./min. The glass transition temperature (Tg) of the polyimide film (30 μm thickness) was determined from the tan δ peak. The results are shown in Table 1.

(4) Thermal expansion coefficient About the polyimide film with a film thickness of 30 μm produced in the same manner as in (3) above, using a thermal / stress / strain measuring device (“TMA / SS6100” manufactured by SII Nanotechnology Co., Ltd.). Then, thermomechanical analysis is performed under the conditions of a load of 0.5 g / film thickness of 1 μm and a heating rate of 10 ° C./min, and an average value of the elongation in the plane direction (X direction) of the polyimide film in the range of 60 to 260 ° C. is obtained. From this value, the linear thermal expansion coefficient (CTE) in the surface direction (X direction) of the polyimide film (30 μm thick) was determined. The results are shown in Table 1.

  As is clear from the results shown in Table 1, any polyesterimide resin (Synthesis Examples 1 to 10) containing the structural unit A composed of the acid anhydride unit and the diamine A unit according to the present invention in a predetermined ratio is used. At room temperature, the resin concentration was 10% by mass and it was soluble in NMP and could be formed into a film. Moreover, Tg was 260 degreeC or more also in any polyesterimide film | membrane, and it turned out that it is a thing with high heat resistance. Furthermore, CTE was 20 ppm / K or less, and it was found that the material had a small dimensional change.

  On the other hand, a polyimide resin not containing an acid anhydride unit according to the present invention (Comparative Synthesis Examples 1 to 7) and a polyimide resin containing only the diamine A unit according to the present invention as a diamine unit (Comparative Synthesis Example 8) are insoluble in NMP. Met. In particular, the polyimide resin obtained in Comparative Synthesis Example 6 swelled in the NMP solution, but was insoluble in NMP. Thus, since the polyimide resins obtained in Comparative Synthesis Examples 1 to 8 were not uniformly dissolved in NMP, it was difficult to measure the reduced viscosity of the solution, and it was difficult to prepare the varnish. The glass transition temperature and the thermal expansion coefficient could not be measured.

  On the other hand, the polyimide resin (Comparative Synthesis Examples 9 to 10) having a diamine A unit content of less than 50 mol% according to the present invention is soluble in NMP at a resin concentration of 10% by mass at room temperature. It was possible. The polyimide film had a Tg of 286 to 298 ° C. and high heat resistance. However, the CTE was 54 to 65 ppm / K, which was inferior in dimensional stability compared to the polyesterimide resin according to the present invention.

Example 1
(1) Preparation of resin varnish 35.0 parts by mass of the polyesterimide resin obtained in Synthesis Example 1, spherical fused silica as an inorganic filler (“SO-25R” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) 65.0 parts by mass and 0.3 part by mass of a silane coupling agent (“A187” manufactured by Nihon Unicar Co., Ltd.) are mixed, NMP is added to the mixture so that the solid content concentration becomes 50% by mass, and high-speed stirring is performed. The apparatus was stirred for 30 minutes to obtain a resin varnish.

(2) Preparation of prepreg The resin varnish obtained in the above (1) was prepared by using a glass woven fabric having a thickness of 90 μm (“E10T cloth” manufactured by Unitika Ltd.) and a glass woven fabric having a thickness of 27 μm (manufactured by Unitika Ltd.). “E03E cloth”) was impregnated and dried in a heating furnace at 150 ° C. for 2 minutes to prepare a prepreg having a thickness of 100 μm and a prepreg having a thickness of 40 μm.

(3) Preparation of copper clad laminate A 12 μm thick copper foil (“3EC-M3-VLP” manufactured by Mitsui Mining & Smelting Co., Ltd.) is laminated on both sides of the 100 μm thick prepreg obtained in (2) above. A copper-clad laminate (thickness: 0.1 mm) having a double-sided copper foil was prepared by heating and pressure molding at a pressure of 3 MPa and a temperature of 260 ° C. for 2 hours.

(4) Production of multilayer printed wiring board The copper-clad laminate obtained in (3) was subjected to through-hole processing using a 0.1 mm drill bit, and then filled with through-holes by plating. Next, etching was performed on both sides of the copper clad laminate to form a circuit, and an inner layer circuit board was produced. The prepreg with a thickness of 40 μm obtained in (2) above is superimposed on the front and back of the inner layer circuit board, and this is vacuum-heated for 2 hours at a temperature of 260 ° C. and a pressure of 3 MPa using a vacuum press. A plate was made.

(5) Fabrication of semiconductor device An opening is provided in the insulating layer (prepreg part having a thickness of 40 μm) of the multilayer printed wiring board obtained in (4) above using a carbonic acid laser device, and the surface of the insulating layer is formed by electrolytic copper plating. An outer layer circuit was formed to achieve conduction between the outer layer circuit and the inner layer circuit. The outer layer circuit was provided with a connecting electrode portion for mounting a semiconductor element. Next, a solder resist (manufactured by Taiyo Ink, PSR4000 / AUS308) is formed as the outermost layer, and the connection electrode portion is exposed by exposure and development so that a semiconductor element can be mounted, and after the nickel gold plating treatment is performed, the multilayer The printed wiring board was cut into a size of 50 mm × 50 mm.

  Next, the semiconductor device was assembled. As a semiconductor element, a TEG chip (size: 15 mm) in which solder bumps are formed of a eutectic of Sn / Pb composition and a circuit protective film is formed of a positive photosensitive resin (“CRC-8300” manufactured by Sumitomo Bakelite Co., Ltd.) × 15 mm, thickness 0.8 mm) was used. First, a flux material was uniformly applied to the solder bumps by a transfer method, and a semiconductor element was mounted on the multilayer printed wiring board using a flip chip bonder device by thermocompression bonding. Next, after melt-bonding the solder bumps in an IR reflow furnace, a liquid sealing resin (“CRP-4152S” manufactured by Sumitomo Bakelite Co., Ltd.) is filled, and the liquid sealing resin is heated at 150 ° C. for 120 minutes. The semiconductor device was produced by curing with Note that the semiconductor element and the multilayer printed wiring board are connected via 300 solder bumps, and the obtained semiconductor device has a daisy chain, whereby the continuity of the connection portion can be confirmed.

(Examples 2 to 10)
A resin varnish was prepared in the same manner as in Example 1 except that 35.0 parts by mass of the polyesterimide resin obtained in Synthesis Examples 2 to 10 were used instead of the polyesterimide resin obtained in Synthesis Example 1, respectively. A prepreg, a copper clad laminate, a multilayer printed wiring board, and a semiconductor device were produced.

(Comparative Example 1)
A resin varnish was prepared in the same manner as in Example 1 except that 35.0 parts by mass of the polyimide resin obtained in Comparative Synthesis Example 10 was used instead of the polyesterimide resin obtained in Synthesis Example 1, and a prepreg, copper A tension laminate, a multilayer printed wiring board, and a semiconductor device were produced.

(Comparative Example 2)
In place of 35.0 parts by mass of the polyesterimide resin, 2,2′-bis (4- (4-maleimidophenoxyphenyl) propane (“BMI-80” manufactured by Kay Chemical Co., Ltd.) as a bismaleimide resin25. 7 parts by mass, the same as in Example 1 except that 9.3 parts by mass of 4,4′-diaminodiphenylsulfone (“4,4′-DAS” manufactured by Mitsui Chemicals Fine Co., Ltd.) was used as the curing agent. A resin varnish was prepared, and a prepreg, a copper clad laminate, a multilayer printed wiring board, and a semiconductor device were produced.

(Comparative Example 3)
Instead of 35.0 parts by mass of the polyesterimide resin, 20.0 parts by mass of biphenylaralkyl novolac epoxy resin (“NC-3000” manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin, and novolak type cyanate resin (Lonza Japan) as a cyanate resin 15.0 parts by mass of “Primaset PT-30” manufactured by Co., Ltd., and 0.15 parts by mass of 2-phenyl-4-methylimidazole (“Curesol 2P4MZ” manufactured by Shikoku Kasei Kogyo Co., Ltd.) are used as these curing agents. A resin varnish was prepared in the same manner as in Example 1 except that a prepreg, a copper clad laminate, a multilayer printed wiring board, and a semiconductor device were produced.

(Comparative Example 4)
A resin varnish was prepared in the same manner as in Comparative Example 1 except that the content of the polyimide resin obtained in Comparative Synthesis Example 10 was changed to 30.0 parts by mass and the content of spherical fused silica was changed to 70.0 parts by mass. A prepreg, a copper clad laminate, a multilayer printed wiring board, and a semiconductor device were produced.

(Comparative Example 5)
The same as Comparative Example 2 except that the content of the bismaleimide resin was changed to 22.0 parts by mass, the content of the curing agent was changed to 8.0 parts by mass, and the content of the spherical fused silica was changed to 70.0 parts by mass. A resin varnish was prepared to prepare a prepreg, a copper clad laminate, a multilayer printed wiring board, and a semiconductor device.

(Comparative Example 6)
The epoxy resin content is 17.1 parts by mass, the cyanate resin content is 12.9 parts by mass, the curing agent content is 0.12 parts by mass, and the spherical fused silica content is 70.0 parts by mass. A resin varnish was prepared in the same manner as in Comparative Example 3 except that the prepreg was changed, and a prepreg, a copper clad laminate, a multilayer printed wiring board, and a semiconductor device were produced.

(Comparative Example 7)
A resin varnish was prepared in the same manner as in Comparative Example 1 except that the content of the polyimide resin obtained in Comparative Synthesis Example 10 was changed to 25.0 parts by mass and the content of spherical fused silica was changed to 75.0 parts by mass. A prepreg, a copper clad laminate, a multilayer printed wiring board, and a semiconductor device were produced.

(Comparative Example 8)
The same as Comparative Example 2 except that the content of the bismaleimide resin was changed to 18.4 parts by mass, the content of the curing agent was changed to 6.6 parts by mass, and the content of the spherical fused silica was changed to 75.0 parts by mass. A resin varnish was prepared to prepare a prepreg, a copper clad laminate, a multilayer printed wiring board, and a semiconductor device.

(Comparative Example 9)
The epoxy resin content is 14.3 parts by mass, the cyanate resin content is 10.7 parts by mass, the curing agent content is 0.10 parts by mass, and the spherical fused silica content is 75.0 parts by mass. A resin varnish was prepared in the same manner as in Comparative Example 3 except that the prepreg was changed, and a prepreg, a copper clad laminate, a multilayer printed wiring board, and a semiconductor device were produced.

  The characteristic evaluation methods of the obtained resin varnish, prepreg, copper-clad laminate, multilayer printed wiring board and semiconductor device are shown below.

(1) Impregnation The cross section of the copper clad laminate (thickness 0.1 mm) was observed using a scanning electron microscope (“JCM-5700” manufactured by JEOL Ltd.). Based on the void area ratio observed in the cross-sectional observation, the impregnation property of the resin varnish was evaluated in the following three stages. The results are shown in Tables 2-3.
A: When the area of the void is less than 10% of the total area of the cross section.
B: When the area of the void is 10 to 30% of the total area of the cross section.
C: When the void area exceeds 30% of the total cross-sectional area.

(2) Glass transition temperature The copper foil of the copper clad laminate (thickness 0.1 mm) was removed by whole surface etching, and a 6 mm × 25 mm test piece was cut out from the obtained laminate, and the laminate was subjected to viscoelastic spectroscopy. Using a meter (“DMS6100” manufactured by SII NanoTechnology Co., Ltd.), dynamic viscoelasticity measurement was performed under the conditions of a frequency of 0.1 Hz and a temperature increase rate of 5 ° C./min, and the glass transition of the laminate from the tan δ peak. The temperature (Tg) was calculated. The results are shown in Tables 2-3.

(3) Coefficient of thermal expansion The copper foil of the copper clad laminate (thickness: 0.1 mm) is removed by whole surface etching, and a 5 mm × 20 mm test piece is cut out from the obtained laminate, and a thermal / stress / strain measuring device ( Thermomechanical analysis is performed under the conditions of a load of 0.5 g / film thickness of 1 μm and a temperature increase rate of 5 ° C./min using SII Nano Technology Co., Ltd. “TMA / SS6100”, and a range of 60 to 260 ° C. The average value of the elongation in the plane direction (X direction) of the laminate was obtained, and the linear thermal expansion coefficient (CTE) in the plane direction (X direction) of the laminate was obtained from this value. The results are shown in Tables 2-3.

(4) Drill workability The state of the cutting edge of the drill blade after drilling 2000 holes at 300,000 revolutions / piece using a 0.1 mm diameter drill blade on a copper clad laminate (thickness 0.1 mm) Was evaluated in the following two stages, and drill workability was evaluated. The results are shown in Tables 2-3.
A: The cutting edge remains, and the drill blade can be regenerated by regrinding.
B: The cutting edge is rounded and it is difficult to regenerate the drill blade.

(5) Warpage amount of multilayer printed wiring board The multilayer printed wiring board is high at a measurement temperature of 25 ° C. or 260 ° C. using a temperature variable laser three-dimensional measuring machine (“LS220-MT100MT50” manufactured by Hitachi Technology & Service Co., Ltd.). The displacement in the vertical direction was measured, and the value of the portion with the largest displacement difference was taken as the amount of warpage of the multilayer printed wiring board. The results are shown in Tables 2-3.

(6) Connection reliability For ten semiconductor devices, the continuity of the connection portion was confirmed by a daisy chain, and the connection reliability was evaluated by the number of defective connections. The results are shown in Tables 2-3.

  As is apparent from the results shown in Table 2, when a polyesterimide resin containing the structural unit A composed of the acid anhydride unit and the diamine unit according to the present invention in a predetermined ratio is used (Examples 1 to 10). The resin varnish is excellent in impregnation, the laminated board has a low CTE of 4 ppm / K or less, the dimensional change is small, the drilling workability is good, the multilayer printed wiring board is small in warpage, and the semiconductor device is Connection reliability was excellent.

  On the other hand, as is clear from the results shown in Table 3, when the polyimide resin not containing the diamine A unit according to the present invention is used (Comparative Example 1), the bismaleimide resin is used (Comparative Example 2), and When an epoxy resin and a cyanate resin are used in combination (Comparative Example 3), the resin varnish is excellent in impregnation property and the drilling property of the laminate plate is good, but the laminate plate has a high CTE of 8 ppm / K or more. The change was large, the multilayer printed wiring board was warped, and some semiconductor devices had poor connection.

  Moreover, when the content rate of an inorganic filler is increased with respect to the resin varnishes obtained in Comparative Examples 1 to 3, respectively (Comparative Examples 4 to 6), the CTE of the laminate is reduced, but it is sufficiently The warp of the multilayer printed wiring board and the connection reliability of the semiconductor device were not sufficiently improved. Moreover, when the polyimide resin not containing the diamine A unit according to the present invention is used (Comparative Example 4) and when the bismaleimide resin is used (Comparative Example 5), the impregnation property of the resin varnish is reduced. When the bismaleimide resin was used (Comparative Example 5) and when the epoxy resin and the cyanate resin were used together (Comparative Example 6), the drillability of the laminate decreased.

  When the content of the inorganic filler is further increased, when the polyimide resin not containing the diamine A unit according to the present invention is used (Comparative Example 7), the impregnation property of the resin varnish is remarkably lowered and used for the evaluation test. A possible prepreg could not be produced. On the other hand, when the bismaleimide resin was used (Comparative Example 8) and when the epoxy resin and the cyanate resin were used together (Comparative Example 9), the CTE of the laminate was further reduced to 4 ppm / K or less. The impregnation property of the resin varnish and the drilling property of the laminate were further lowered, and the connection reliability of the semiconductor device was not sufficiently improved. Further, the warpage of the multilayer printed wiring board was improved and was sufficient at 25 ° C., but not sufficient at 260 ° C.

  As explained above, according to the present invention, a polyesterimide resin that is soluble in a solvent, exhibits good impregnation before curing, and has a high glass transition temperature and a low linear thermal expansion coefficient after curing. An imide resin composition can be obtained. When such a polyesterimide resin composition is used, the laminate of the present invention having excellent heat resistance, little warping even at high temperatures, and good drilling workability can be obtained.

  Therefore, since such a laminated plate does not easily increase the coefficient of linear thermal expansion even in the semiconductor mounting temperature region and can reduce the warpage of the substrate during mounting, a thin system-in-package substrate or semiconductor package It is particularly useful as a substrate for an automobile.

Claims (6)

Following formula (1):

(In the formula (1), Ar ¹ and Ar ² represent an aryl group, which may be the same or different, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group and an alkoxy group. Any one of the groups, X represents —NH—C (═O) — or —C (═O) —NH—, n is 1 or 2, and when n is 2, the formula ( 1) The two Xs present in them may be the same or different.)
A structural unit A represented by:
Following formula (2):

(In the formula (2), Ar ¹ and Ar ² are the same as the Ar ¹ and Ar ² in the formula (1), Ar ³ represents a divalent group having an aromatic ring or aliphatic ring .)
A polyesterimide resin composition comprising: a polyesterimide resin containing a structural unit B represented by the formula B; and a content of the structural unit A of 50 to 95 mol%, and an inorganic filler. The Ar ¹ and Ar ^{2 in the} formula (1) and the formula (2) are each independently a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group. The polyesterimide resin composition as described. Ar ³ in the formula (2) is represented by the following formulas (I) to (VIII):

(K in the formula (I) is an integer of 0 to 5, and R ³ and R ⁴ in the formula (III) are each independently a hydrogen atom, an alkyl group, a halogenated alkyl group or a hydroxyl group. R ⁵ and R ⁶ in formula (IV) each independently represent a hydrogen atom or an alkyl group, and R ⁷ and R ^{8 in} formula (V) each independently represent a hydrogen atom, a halogen atom or an alkyl group Represents any one of a group and a hydroxyl group, and R ⁹ and R ^{10 in} formula (VIII) each independently represent any one of a hydrogen atom, a halogen atom, an alkyl group, and a hydroxyl group.)
The polyesterimide resin composition according to claim 1, wherein the polyesterimide resin composition is any one of divalent groups represented by the formula:   A prepreg obtained by impregnating a base material with the polyesterimide resin composition according to any one of claims 1 to 3.   A laminate comprising a layer formed by subjecting the prepreg according to claim 4 to a heat treatment.   A semiconductor device comprising: the laminated board according to claim 5; and a semiconductor element disposed on the laminated board.

Images