JP2002080718A - Resin composition for insulating film and insulating film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an insulating film having excellent heat characteristics, electric characteristics and water absorption, especially an extremely low relative dielectric constant in an application of semiconductor. SOLUTION: This resin composition for an insulating film comprises a polyamide and an oligomer having a repeating unit of a specific structure as essential components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating material having excellent electrical, thermal and mechanical properties.
It can be applied as an interlayer insulating film for semiconductors, a protective film, an interlayer insulating film for multilayer circuits, a cover coat for a flexible copper clad board, a solder resist film, a liquid crystal alignment film, and the like.

[0002]

2. Description of the Related Art In a semiconductor material, an inorganic material, an organic material, and the like are used in various parts according to required characteristics. For example, as an interlayer insulating film for a semiconductor, an inorganic oxide film such as silicon dioxide manufactured by a chemical vapor deposition method is used. However, in recent years, the speeding up of semiconductors,
With the increase in performance, the inorganic oxide film as described above has a problem that the relative dielectric constant is high. As one of the improvement means, application of an organic material is being studied.

[0003] Organic materials for semiconductor applications include heat resistance,
A polyimide resin having excellent electrical characteristics, mechanical characteristics, and the like is used, and is used for a solder resist, a coverlay, a liquid crystal alignment film, and the like. However, since polyimide resins generally have two carbonyl groups on the imide ring, there are problems in water absorption and electrical properties. To solve these problems, attempts have been made to improve water absorption and electrical properties by introducing fluorine or a fluorine-containing group into an organic polymer, and some of them have been put to practical use. In addition, there is a polybenzoxazole resin exhibiting better performance in heat resistance, water absorption, and electrical characteristics than polyimide resin, and application to various fields has been attempted. For example, those having a structure consisting of 4,4′-diamino-3,3′-dihydroxybiphenyl and terephthalic acid,
Examples include a polybenzoxazole resin having a structure composed of 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and terephthalic acid.

However, more severe heat resistance, electrical characteristics,
In the advanced field where improvement of water absorption etc. is required, a material satisfying all such requirements has not yet been obtained. In other words, although excellent heat resistance is exhibited, electric characteristics such as dielectric constant are not sufficient. Further, although electric characteristics are improved by introducing fluorine, heat resistance is lowered. In particular, when an organic material is applied as an interlayer insulating film for a semiconductor, heat resistance comparable to an inorganic material,
Mechanical characteristics and water absorption are required, and further lowering of the dielectric constant is required.

[0005] In response to such demands for higher performance, a method of reducing the density and lowering the relative dielectric constant by forming fine holes in the inorganic oxide film, which is an inorganic material, has been studied. I have. The relative permittivity of air is 1, and reducing the relative permittivity by introducing air into the film is disclosed in US Pat. No. 3,883,452 to Scheuerlein et al. (May 1, 1975).
It is inferred from a method for producing a foamed polymer having an average pore diameter of about 20 μm (issued on March 3). However, in order to make an effective insulator by introducing air into the film, the film thickness needs to be on the order of sub-micrometer, has an averaged relative dielectric constant, and the mechanical properties of the film itself Must be able to withstand each step. At present, an inorganic material that overcomes such a problem has not yet been obtained.

On the other hand, in the case of organic materials, techniques for obtaining submicrometer-order micropores are disclosed in Hedr.
U.S. Pat. No. 5,776,990 to ick et al. (199).
(July 7, 2008) discloses that a block copolymer is formed into a resin having fine pores on the order of sub-micrometer. It is known that block copolymers undergo phase separation on the order of sub-micrometer (T.
Hashimoto, M.Shibayama, M.Fujimura and H.Kawai, "Mi
crophase Separation and the Polymer-polymer Interp
hase in Block Polymers "in" Block Copolymers-Scien
ce and Technology ", p.63, Ed.By DJMeier (Academic
Pub., 1983)), and it is generally well known in the field of polymer chemistry that polymers having a low ceiling temperature are easily decomposed. However, in order to obtain a resin composition having micropores while satisfying not only the relative permittivity but also the mechanical properties, electrical properties, water absorption resistance, and heat resistance, it is necessary to use a resin, a blocking technique, and a thermally decomposable component. Combinations are very limited in their choice, and none of them can satisfy all the characteristics.

[0007]

SUMMARY OF THE INVENTION The present invention provides a resin composition for an insulating film which maintains excellent heat resistance and enables a low dielectric constant in a semiconductor application, and an insulating film using the same. With the goal.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above-mentioned conventional problems, and as a result, have found that a resin composition containing a polyamide having a specific structure and an oligomer as essential components has been obtained. Have found that the object of the present invention can be satisfied,
Further studies have led to the completion of the present invention.

That is, the present invention is a resin composition for an insulating film comprising a polyamide having a repeating unit represented by the general formula (1) and an oligomer as essential components.

[0010]

Embedded image (Where m and n in the formula are m> 0, n ≧ 0, 2 ≦ m
+ N ≦ 1000 and an integer satisfying 0.05 ≦ m / (m + n) ≦ 1. X represents a formula (2), Y represents a formula (3), and Z represents a group selected from the structure represented by the formula (4). )

[0011]

Embedded image

[0012]

Embedded image

[0013]

Embedded image (However, in the formulas (2) and (4), X ₁ represents a group selected from the structure represented by the formula (5).
In the structures of the formulas (3), (4) and (5), the hydrogen atom on the benzene ring is a methyl group, an ethyl group, a propyl group,
It may be substituted with at least one group selected from the group consisting of an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a fluorine atom, and a trifluoromethyl group. )

[0014]

Embedded image

Further, the present invention is an insulating film having a main structure of polybenzoxazole obtained by subjecting the resin composition to a heat treatment to cause a condensation reaction and a cross-linking reaction, and having fine pores.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a tran skeleton which is crosslinked by heating is introduced into the main chain of a polyamide, and the hydroxyamide structure is converted into polybenzoxazole by a ring-closing reaction, and the tran skeleton is crosslinked to form a resin. By making the structure three-dimensional, a resin having high heat resistance can be obtained. The other essential component, the oligomer, is thermally decomposed during the heating of the resin and volatilized, forming micropores in the polybenzoxazole resin film, and a porous insulating material that achieves both heat resistance and electrical characteristics. Obtaining the membrane is the gist of the present invention.

In the present invention, the polyamide, which is an essential component, comprises at least one bisaminophenol compound having any of the structures represented by the formula (2),
Using a dicarboxylic acid having a tran skeleton having a structure represented by the formula (3) or as the dicarboxylic acid, a combination of the dicarboxylic acid and a dicarboxylic acid having any of the structures represented by the formula (4) And the conventional acid chloride method,
It can be obtained by a method such as an activated ester method or a condensation reaction in the presence of a dehydrating condensing agent such as polyphosphoric acid or dicyclohexylcarbodiimide. Also, by combining this polyamide having a tran skeleton with another polyamide of a type that does not undergo a cross-linking reaction, which has been conventionally used, to form an interpenetrating network structure, it is also possible to obtain a resin having high heat resistance. It is possible. In this case, the polyamide having no tolan skeleton is obtained by combining at least one of the bisaminophenol compounds having any of the structures represented by the formula (2) with the structure represented by the formula (4). It can be obtained by a similar method using at least one of the dicarboxylic acids having any one of them.

The bisaminophenol compound having a structure represented by the formula (2) used in the present invention includes 2,4
-Diaminoresorcinol, 4,6-diaminoresorcinol, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-
(Amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) propane, 3,3′- Diamino-4,4
'-Dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, 3,3'
-Diamino-4,4'-dihydroxybiphenyl, 4,4 '
-Diamino-3,3'-dihydroxybiphenyl, 9,9
-Bis (4-((4-amino-3-hydroxy) phenoxy) phenyl) fluorene, 9,9-bis (4-
((3-amino-4-hydroxy) phenoxy) phenyl) fluorene, 9,9-bis ((4-amino-3-hydroxy) phenyl)) fluorene, 9,9-bis ((3-amino-4-hydroxy ) Phenyl)) fluorene, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 4,4'-diamino-3,3'-dihydroxyphenyl ether, 2,2-bis (3-amino-4-
Hydroxy-2-trifluoromethylphenyl) propane, 2,2-bis (4-amino-3-hydroxy-2-
Trifluoromethylphenyl) propane, 2,2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) propane, 2,2-bis (4-amino-3
-Hydroxy-5-trifluoromethylphenyl) propane, 2,2-bis (3-amino-4-hydroxy-6)
-Trifluoromethylphenyl) propane, 2,2-bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) propane, 2,2-bis (3-amino-
4-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (4-amino-3
-Hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-
(Hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (3-amino-4- (Hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 3,3′-diamino-4,4′- Dihydroxy-2,2'-bis (trifluoromethyl) biphenyl,
4,4'-diamino-3,3'-dihydroxy-2,2'-bis (trifluoromethyl) biphenyl, 3,3'-diamino-4,4'-dihydroxy-5,5'-bis (trifluoro Methyl) biphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-bis (trifluoromethyl) biphenyl, 3,3'-diamino-4,4'-dihydroxy-
6,6′-bis (trifluoromethyl) biphenyl,
4'-diamino-3,3'-dihydroxy-6,6'-bis (trifluoromethyl) biphenyl and the like. These may be used alone or in combination of two or more.

Examples of the dicarboxylic acid having a tran skeleton having the structure represented by the formula (3) used in the present invention include:
2,2′-trandicarboxylic acid, 2,3′-trandicarboxylic acid, 2,4′-trandicarboxylic acid, 3,3′-trandicarboxylic acid, 3,4′-trandicarboxylic acid,
4′-transdicarboxylic acid, and the like, and from the performance of the obtained polyamide, 3,4′-transdicarboxylic acid,
And 4,4'-trandicarboxylic acid are particularly preferred.
These may be used alone or in combination of two or more.

Examples of the dicarboxylic acid having a structure represented by the formula (4) used in the present invention include isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, and 3,4 '
-Biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-sulfonylbisbenzoic acid, 3, 4′-sulfonylbisbenzoic acid, 3,3′-sulfonylbisbenzoic acid,
4,4'-oxybisbenzoic acid, 3,4'-oxybisbenzoic acid, 3,3'-oxybisbenzoic acid, 2,2-bis (4
-Carboxyphenyl) propane, 2,2-bis (3-
(Carboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-
Bis (3-carboxyphenyl) hexafluoropropane, 2,2'-dimethyl-4,4'-biphenyldicarboxylic acid, 3,3'-dimethyl-4,4'-biphenyldicarboxylic acid, 2,2'-dimethyl- 3,3′-biphenyldicarboxylic acid, 2,2′-bis (trifluoromethyl) -4,4′-biphenyldicarboxylic acid, 3,3′-bis (trifluoromethyl) -4,4′-biphenyldicarboxylic acid 2,2′-bis (trifluoromethyl) -3,3′-biphenyldicarboxylic acid, 9,9-bis (4- (4-carboxyphenoxy) phenyl) fluorene, 9,9-bis (4- (3 −
Carboxyphenoxy) phenyl) fluorene, 4,
4'-bis (4-carboxyphenoxy) biphenyl,
4,4'-bis (3-carboxyphenoxy) biphenyl, 3,4'-bis (4-carboxyphenoxy) biphenyl, 3,4'-bis (3-carboxyphenoxy)
Biphenyl, 3,3'-bis (4-carboxyphenoxy) biphenyl, 3,3'-bis (3-carboxyphenoxy) biphenyl, 4,4'-bis (4-carboxyphenoxy) -p-terphenyl, 4'-bis (4
-Carboxyphenoxy) -m-terphenyl, 3,
4'-bis (4-carboxyphenoxy) -p-terphenyl, 3,3'-bis (4-carboxyphenoxy)
-P-terphenyl, 3,4'-bis (4-carboxyphenoxy) -m-terphenyl, 3,3'-bis (4
-Carboxyphenoxy) -m-terphenyl, 4,
4'-bis (3-carboxyphenoxy) -p-terphenyl, 4,4'-bis (3-carboxyphenoxy)
-M-terphenyl, 3,4'-bis (3-carboxyphenoxy) -p-terphenyl, 3,3'-bis (3
-Carboxyphenoxy) -p-terphenyl, 3,
4'-bis (3-carboxyphenoxy) -m-terphenyl, 3,3'-bis (3-carboxyphenoxy)
-M-terphenyl, 3-fluoroisophthalic acid, 2-
Fluoroisophthalic acid, 2-fluoroterephthalic acid,
2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,
Examples thereof include 6-tetrafluoroterephthalic acid and 5-trifluoromethylisophthalic acid, which may be used alone or in combination of two or more.

In the polyamide of the present invention, m and n in the formula (1), which is the number of repeating units having a tran skeleton and the number of repeating units having no tran skeleton, are: m> 0,
n ≧ 0, 2 ≦ m + n ≦ 1000, 0.05 ≦ m / (m +
n) An integer satisfying ≦ 1. The sum of m and n is preferably 5 or more and 100 or less. Here, if the sum of m and n is less than 2, the film-forming property is reduced, and the mechanical strength of the film becomes insufficient. On the other hand, if it exceeds 1,000, the molecular weight becomes too large, making it difficult to dissolve in a solvent, or even if dissolved, it becomes a viscous varnish, which is not suitable for practical use. m and n are 0.05 ≦ m
An integer that satisfies / (m + n) ≦ 1 is essential, and more preferably satisfies 0.5 ≦ m / (m + n) ≦ 1. When 0.05> m / (m + n), it means that the number of repeating units having a tran skeleton is small, and since the number of crosslinking reaction sites is small, heat resistance is not improved, which is not preferable. Further, the repeating units m and n may be represented by -m-n-m-m-n- even in a block shape as the arrangement is typically represented by -m-m-m-n-n-n-. It may be in a random form as typically represented by n-.

In the present invention, as a method for producing a polyamide which is an essential component, a conventional method such as an acid chloride method, an activated ester method, a condensation reaction in the presence of a dehydrating condensing agent such as polyphosphoric acid and dicyclohexylcarbodiimide, and the like are used. I can do it. For example, in the acid chloride method, the acid chloride to be used is, first, a dicarboxylic acid and an excess amount of thionyl chloride in the presence of a catalyst such as N, N-dimethylformamide.
The reaction can be carried out at room temperature to 130 ° C., excess thionyl chloride is distilled off by heating and reduced pressure, and the residue can be obtained by recrystallization with a solvent such as hexane. When the dicarboxylic acid chloride thus produced and the other dicarboxylic acid are used in combination, the acid chloride obtained in the same manner is usually used together with a bisaminophenol compound together with N-
A polyamide can be obtained by dissolving in a polar solvent such as methyl-2-pyrrolidone or N, N-dimethylacetamide and reacting at room temperature to -30 ° C in the presence of an acid acceptor such as pyridine.

The dicarboxylic acid having a tolan skeleton having the structure represented by the formula (3) used in the present invention is prepared by, for example, preparing a stilbene from a benzoate derivative and then preparing a tolan skeleton. Alternatively, it can be obtained by a method of synthesizing a benzoate derivative and a phenylethynyl derivative by introducing a trans skeleton using a Heck reaction.

In the present invention, the oligomer, which is the other essential component, may be any oligomer as long as it is thermally decomposed at a temperature lower than the thermal decomposition temperature of the polyamide and the decomposition product is vaporized. Specifically, polyoxymethylene, polyoxyethylene, polyoxypropylene, polyoxymethylene-oxyethylene copolymer, polyoxymethylene-oxypropylene copolymer,
Polyoxyalkylene such as polyoxyethylene-oxypropylene copolymer and polymethyl methacrylate, poly α-methylstyrene, polystyrene, the structure of the repeating unit is methylene, ethylene, propylene, butylene, polyurethane, polyamide, polyester, polycarbonate , Polyether urethane, polyether amide. Preferable examples include polyether esters, polyether carbonates, and polyamide esters.
If necessary, those having a functional group such as a hydroxyl group, an amino group, a nitro group, a carboxy group, a cyano group, or a methacryl group introduced at one or both ends can be used. It is also possible to react with a carboxy group, an amino group, a hydroxyl group, or a hydroxyl group in the main chain structure at the terminal of the polyamide resin and use it as a copolymer. These organic compounds may be used alone or in combination of two or more.

The oligomer has a number average molecular weight of 100 to
Those having a range of 10,000 are preferred. If the molecular weight is less than 100, the voids after decomposition and vaporization are small and easily crushed, so that a reduction in the relative dielectric constant cannot be exhibited.
On the other hand, if the molecular weight exceeds 10,000, the voids become too large, and the mechanical properties of the insulating film are extremely deteriorated, which causes a problem that the insulating film cannot be put to practical use.

The amount of the oligomer is preferably 5 to 40 parts by weight based on 100 parts by weight of the polyamide. If the amount is less than 5 parts by weight, the porosity in the insulating film is small, and it is insufficient to reduce the dielectric constant. If the amount exceeds 40 parts by weight, the porosity in the film increases and the mechanical strength of the film decreases. It is not preferable because it extremely decreases or the gap becomes continuous and non-uniform, and the dielectric constant varies from place to place.

As a method of using the resin composition for an insulating film of the present invention, it is possible to dissolve the resin composition in an appropriate organic solvent and use it as a varnish. Specifically, the resin composition is dissolved in an organic solvent, and a suitable support, for example,
Apply to glass, fiber, metal, silicon wafer, ceramic substrate, etc. Examples of the application method include dipping, screen printing, spraying, spin coating, roll coating, and the like. After application, the coating is heated and dried to volatilize the solvent, and a tack-free coating film can be obtained.

As the organic solvent for dissolving the resin composition for an insulating film of the present invention, a solvent that completely dissolves solids is preferable. For example, N-methyl-2-pyrrolidone, γ-
Butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate,
Methyl-1,3-butylene glycol acetate, 1,3
-One or a mixture of butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, tetrahydrofuran, etc. Can be used. The amount used is not critical as long as the polyamide and the organic compound can be completely dissolved, and can be adjusted according to the intended use.

The polyamide in the resin composition of the present invention comprises:
By further heating the coating film obtained as described above at a temperature of 300 ° C., preferably 350 ° C. or higher, a cyclization condensation reaction and a crosslinking reaction occur, and the oligomer is
At this time, pyrolysis decomposes and the decomposed product is vaporized and volatilized to form fine pores in the resin film having polybenzoxazole as a main structure, whereby a porous insulating film can be obtained.

In the insulating film having the main structure of polybenzoxazole of the present invention and having fine holes, the size of the fine holes is at least 20 nm or less, preferably 5 nm or less when used for an interlayer insulating film for semiconductors. Desirably. If the pore size is larger than 20 nm, the porosity of the insulating film used between the wirings will be non-uniform, and the electrical characteristics will not be constant. In addition, problems such as a decrease in mechanical strength of the film and an adverse effect on adhesiveness occur.

If necessary, the resin composition of the present invention may contain, as various additives, a surfactant, a coupling agent represented by a silane compound, a radical initiator which generates oxygen radicals or sulfur radicals by heating, and the like. It can be used for forming interlayer insulating films for semiconductors, protective films, interlayer insulating films for multilayer circuits, cover coats for flexible copper clad boards, solder resist films, liquid crystal alignment films, and the like. Further, the polyamide in the present invention can be used as a photosensitive resin composition by being used together with a naphthoquinonediazide compound as a photosensitive agent.

[0032]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited thereto.

Using the films prepared in Examples and Comparative Examples, the dielectric constant, heat resistance, and glass transition temperature were measured by the following methods for evaluating the characteristics. In addition, the presence / absence of micropores and the diameter of the pores were observed using a transmission electron microscope (TEM). The results are shown in Table 1. 1. Relative permittivity According to JIS-K6911, at a frequency of 100 KHz,
Hewlett-Packard HP-4284A Pre
The measurement was performed using a cision LCR meter. 2. Heat resistance TG / DTA220 manufactured by Seiko Instruments Inc.
, The temperature at a weight loss of 5% was measured under a flow rate of nitrogen gas of 200 mL / min and a temperature rising rate of 10 ° C./min. 3. Glass transition temperature (Tg) Using DMS6100 manufactured by Seiko Instruments Inc., under a flow of nitrogen gas at 300 mL / min, measurement frequency 1
The measurement was performed in a tensile mode under the conditions of Hz and a heating rate of 3 ° C./min, and the peak top temperature of the loss tangent (tan δ) was defined as the glass transition temperature. 4. A 5 cm square test film having a thickness of 10 μm and a water absorption of 10 μm were immersed in pure water at 23 ° C. for 24 hours to calculate a weight change rate.

(Synthesis Example 1) 2,2-bis (3-amino-
4-hydroxyphenyl) hexafluoropropane 3
6.6 g (0.1 mol) was dissolved in 100 g of dried dimethylacetamide, and 19.8 g of pyridine (0.25 m
After addition of 11.5 g (0.049 mol) of isophthalic acid chloride and 14.9 g (0.04 mol) of 3,4′-trandicarboxylic acid chloride to 35 g of γ-butyrolactone.
049 mol) was dissolved in dry nitrogen at −15.
The mixture was added dropwise at 30 ° C. over 30 minutes. After completion of the dropwise addition, the temperature was returned to room temperature, and the mixture was stirred at room temperature for 5 hours. Thereafter, the reaction solution was dropped into 3 liters of ion-exchanged water, and the precipitate was collected and dried to obtain 53 g of polyamide. The number average molecular weight (Mn) of the obtained polyamide was determined to be 17000 by polystyrene conversion using GPC manufactured by Tosoh Corporation.

(Synthesis Example 2) In Synthesis Example 1, 11.5 g (0.049 mol) of isophthalic chloride and 3,3
14.9 g of 4'-trandicarboxylic acid chloride (0.04
22.8 g of isophthalic chloride instead of 9 mol)
(0.097 mol) and 47 g of polyamide were obtained in the same manner as in Synthesis Example 1 except that the amount was changed to 0.3 g (0.001 mol) of 3,4′-trandicarboxylic acid chloride. The number average molecular weight (Mn) of the obtained polyamide was 15,000 as calculated as polystyrene using GPC manufactured by Tosoh Corporation.

(Synthesis Example 3) In Synthesis Example 1, 11.5 g (0.049 mol) of isophthalic chloride and 3,3
14.9 g of 4'-trandicarboxylic acid chloride (0.04
Except for using 29.7 g (0.098 mol) of 4,4′-tolandicarboxylic acid chloride instead of 9 mol), 53 g of polyamide was obtained in the same manner as in Synthesis Example 1. The number average molecular weight (Mn) of the obtained polyamide was determined to be 20,000 by polystyrene conversion using GPC manufactured by Tosoh Corporation.

Example 1 Polyamide 1 obtained in Synthesis Example 1
00 parts by weight of polyoxypropylene (number average molecular weight 7
500) together with 5 parts by weight, was dissolved in 200 parts by weight of N-methyl-2-pyrrolidone, and filtered through a 0.2 μm Teflon (registered trademark) filter to obtain a varnish. This varnish was applied on a glass plate using a doctor knife. Then, in an oven, 70 ° C / 1 hour, 150 ° C / 30
Then, the mixture was heated in the order of 300 ° C./2 hours and 375 ° C./1 hour to obtain a film having a thickness of 10 μm.

(Example 2) Polyamide 1 obtained in Synthesis Example 1
00 parts by weight of polyoxypropylene (number average molecular weight 7
500) dissolved in 200 parts by weight of N-methyl-2-pyrrolidone together with 25 parts by weight, and
A film was obtained.

(Example 3) Polyamide 1 obtained in Synthesis Example 1
00 parts by weight were dissolved in 200 parts by weight of N-methyl-2-pyrrolidone together with 15 parts by weight of poly-α-methylstyrene (number average molecular weight 2500), and a film was obtained in the same manner as in Example 1.

Example 4 Polyamide 1 obtained in Synthesis Example 3
00 parts by weight together with 15 parts by weight of a polyoxyethylene-oxypropylene copolymer (number average molecular weight 3500),
The film was dissolved in 200 parts by weight of N-methyl-2-pyrrolidone, and a film was obtained in the same manner as in Example 1 below.

Example 5 Polyamide 1 obtained in Synthesis Example 3
00 parts by weight were dissolved in 200 parts by weight of N-methyl-2-pyrrolidone together with 15 parts by weight of polymethyl methacrylate (number average molecular weight 5000), and a film was obtained in the same manner as in Example 1 below.

Comparative Example 1 Polyamide 1 obtained in Synthesis Example 3
00 parts by weight were dissolved in 200 parts by weight of N-methyl-2-pyrrolidone, and a film was obtained in the same manner as in Example 1 below.

Comparative Example 2 Polyamide 1 obtained in Synthesis Example 2
00 parts by weight of polyoxypropylene (number average molecular weight:
7500) was dissolved in 200 parts by weight of N-methyl-2-pyrrolidone together with 25 parts by weight, and a film was obtained in the same manner as in Example 1 below.

Comparative Example 3 Polyamide 1 Obtained in Synthesis Example 1
00 parts by weight of polyoxypropylene (number average molecular weight:
7500) was dissolved in 200 parts by weight of N-methyl-2-pyrrolidone together with 50 parts by weight, and a film was obtained in the same manner as in Example 1 below.

Comparative Example 4 Polyamide 1 Obtained in Synthesis Example 3
00 parts by weight together with 15 parts by weight of polymethyl methacrylate (number average molecular weight: 200000) and N-methyl-2
-Dissolved in 200 parts by weight of pyrrolidone to obtain a film in the same manner as in Example 1.

[0046]

[Table 1]

From the evaluation results of Examples and Comparative Examples summarized in Table 1, the resin composition of the present invention is capable of lowering the dielectric constant while maintaining excellent heat resistance and low water absorption. Understand.

[0048]

Industrial Applicability The resin composition for an insulating film of the present invention can achieve excellent thermal characteristics, electrical characteristics, and water absorption, and in particular, can form an insulating film having an extremely low dielectric constant. It can be suitably used for applications such as interlayer insulating films for semiconductors, protective films, interlayer insulating films for multilayer circuits, cover coats for flexible copper clad boards, solder resist films, and liquid crystal alignment films.

Continued on the front page F term (reference) 4J002 CG002 CH052 CK002 CL002 CM011 4J043 PA04 QB15 QB21 QB34 SA54 TA47 UA121 UA122 UA131 UA132 UA141 UA142 UA151 UA152 UA161 UA162 UA231 UA232 UA261 UA1 UB031 UB031 5F058 AA04 AA10 AC10 AF04 AG01 AH02

Claims (7)

[Claims] 1. A resin composition for an insulating film, comprising a polyamide having a repeating unit represented by the general formula (1) and an oligomer as essential components. Embedded image (Where m and n in the formula are m> 0, n ≧ 0, 2 ≦ m
+ N ≦ 1000 and an integer satisfying 0.05 ≦ m / (m + n) ≦ 1. X represents a formula (2), Y represents a formula (3), and Z represents a group selected from the structure represented by the formula (4). ) Embedded image Embedded image (However, in the formulas (2) and (4), X ₁ represents a group selected from the structure represented by the formula (5).
In the structures of the formulas (3), (4) and (5), the hydrogen atom on the benzene ring is a methyl group, an ethyl group, a propyl group,
It may be substituted with at least one group selected from the group consisting of an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a fluorine atom, and a trifluoromethyl group. ) 2. The oligomer is a polyoxyalkylene,
Polymethyl methacrylate, poly α-methyl styrene,
The resin composition for an insulating film according to claim 1, wherein the resin composition is at least one selected from the group consisting of polystyrene and polystyrene. 3. The oligomer is a polyurethane, polyamide, polyester, polycarbonate, polyether urethane, polyether amide, polyether ester,
The resin composition for an insulating film according to claim 1, wherein the resin composition is at least one selected from the group consisting of polyether carbonate and polyamide ester. 4. The resin composition for an insulating film according to claim 1, wherein the oligomer has a number average molecular weight of 100 to 10,000. 5. The method according to claim 1, wherein 5 to 40 parts by weight of the oligomer is blended with respect to 100 parts by weight of the polyamide.
Or the resin composition for an insulating film according to 4. 6. A polybenzoxazole obtained by subjecting the resin composition for an insulating film according to any one of claims 1 to 5 to a heat treatment to cause a condensation reaction and a cross-linking reaction to have a main structure and a fine structure. An insulating film having holes. 7. The insulating film according to claim 6, wherein the size of the fine holes in the insulating film is 20 nm or less.