JP2001006437A - Low dielectric resin composition and circuit laminated board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition having a low dielectric constant and a low dielectric contact characteristic adapted to be used for printed wiring, excellent in its bonding characteristic to a metal material, and has extremely less scattering of resin upon work by containing bisimide compound or bismaletmide compound in at least one polyimide compound having a specified gradient ratio. SOLUTION: This composition contains 100 parts by weight of at least one polyimide composed of 100-40 mol.% of at least one kind of structural units of Formula I and 0-60 mol.% of at least one kind of structural units of Formula II, and 1-100 parts by weight of at least one kind of compounds of Formula III or IV. In Formulae I, III, IV, Ar is a divalent group selected from the structure of Formula V or the like having an aromatic ring. In Formula II, R is -CH2OC6H4- where an alkylene group or methylene group of C is bonded to Si. In formulae III, IV, R5-7 is H, Cl, Br, carboxyl, C1-4 alkyl or alkoxy.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-dielectric resin having a low dielectric constant and a low dielectric loss tangent for use in printed wiring, excellent in adhesion to metal, and having very little resin scattering during punching and cutting operations. The present invention relates to a composition, a laminate, a metal-clad laminate, and the like.

[0002]

2. Description of the Related Art In recent years, signal speeds and operating frequencies of electronic systems have been dramatically increased, so that electronic systems used in a high-frequency region have excellent heat resistance, a low dielectric constant, and a low dielectric loss tangent. Laminates such as resin and prepreg, metal-clad laminates and the like are desired. A laminate using a low dielectric material, a metal-clad laminate, or the like can increase the propagation speed of an electric signal, and thus can process a signal at a higher speed.

[0003]

Fluororesins and polyphenylene ether resins have been proposed as resins having a low dielectric constant. However, there have been problems such as poor workability and poor adhesion and lack of reliability. Therefore, epoxy-modified polyphenylene ether or polyphenylene ether-modified epoxy has been proposed for the purpose of improving workability and adhesiveness. However, the epoxy resin has a high dielectric constant, and satisfactory characteristics have not been obtained. A curable resin composition prepared by blending a polyphenylene ether resin and a polyfunctional cyanate ester resin, and other resins, adding a radical polymerization initiator, and performing a preliminary reaction (Japanese Patent Laid-Open No. 57-185350).
However, the decrease in the dielectric constant was insufficient. Further, a polybutadiene resin containing thermosetting 1,2-polybutadiene as a main component has a low dielectric constant, but is inferior to an adhesive and has insufficient heat resistance. Composition containing 5 to 20 parts by weight of 1,2-polybutadiene resin, 5 to 10 parts by weight of a crosslinkable monomer and a radical crosslinking agent per 100 parts by weight of polyphenylene ether resin (JP-A-61-8361)
No. 224) is known, but the molecular weight of several thousand
-When polybutadiene resin is used, stickiness remains when the solvent is removed from the composition, and is applied to a glass substrate or the like,
Since the prepreg obtained by impregnation cannot maintain a tack-free state, there is a practical problem. On the other hand, there is a method using 1,2-polybutadiene having a high molecular weight in order to eliminate stickiness, but the solubility in a solvent is reduced, the solution becomes high in viscosity and the fluidity is reduced, which is a practical problem. A low dielectric laminate and a copper-clad laminate (Japanese Patent No. 2578097) in which a cloth made of a fluorocarbon fiber is impregnated with a thermosetting resin have been proposed. However, in order to improve the adhesion between the fluorocarbon fiber and the thermosetting resin. Due to the necessity of treating the surface of the fluorocarbon fiber and the high price of the fluorocarbon fiber, the final laminate and the copper-clad laminate are very expensive and have not been put to practical use.

The present invention has been made to solve the above problems, and has a low dielectric constant and a low dielectric loss tangent for use in printed wiring, has excellent adhesion to metal, and has very little scattering of resin during operation. An object of the present invention is to provide a low dielectric resin composition, a laminate using the same, a metal-clad laminate, and the like.

[0005]

Means for Solving the Problems The low dielectric resin composition according to the present invention comprises a component (a) and a component (b). Component (a): 100 to 40 mol% of at least one structural unit represented by the following formula (1a) and 0 to 60 mol% of at least one structural unit represented by the following formula (1b) At least one or more polyimides. Component (b): at least one selected from compounds represented by the following formulas (2) and (3).

Embedded image (In the formula (1a), Ar represents a divalent group selected from the following structures having an aromatic ring. In the formula (1b), R represents 1 carbon atom.)
-CH ₂ OC ₆ H ₄ — in which an alkylene group or methylene group of 10 to 10 is bonded to Si, and n means an integer of 1 to 20. )

Embedded image (In the formula, R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group. It cannot be an atom.)

Embedded image(Wherein, Ar is selected from the above structures having an aromatic ring
Represents a divalent group;^Five , R⁶And R⁷Are the same
May be different, hydrogen, chlorine, bromine,
Carboxyl group, alkyl group having 1 to 4 carbon atoms or alcohol
Shows a xy group. )

Here, it is desirable that a filler having a particle size of 1 μm or less is contained in an amount of 5 to 70% by weight of the total solid.
Further, it is desirable that the component (b) is blended in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the component (a). It is desirable that the dielectric constant in a cured state is 3.0 or less.

A prepreg according to the present invention comprises the above-described low dielectric resin composition and a fiber reinforcing material. The laminate of the present invention refers to a laminate in which a plurality of prepregs are laminated. The metal-clad laminate of the present invention has a metal layer formed on one or both sides of the above-described prepreg or laminate. As the fiber reinforcing material, a woven or non-woven fabric made of fibers selected from aramid fibers, aromatic polyester fibers, and tetrafluorocarbon fibers is desirable. The metal layer is preferably made of at least one selected from copper, white copper, silver, iron, 42 alloy, and stainless steel.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the first low dielectric resin composition will be described. The first low dielectric resin composition is composed of a component (a) polyimide and a component (b) bisimide-based compound. The polyimide used in the present invention has the formula (1)
a) at least one of the structural units represented by a)
0 mol%, and 0 to 60 mol% of at least one structural unit represented by the formula (1b). That is, as the component (a), only a polyimide composed of the structural unit represented by the formula (1a) may be used, or a polyimide composed of the structural unit represented by the formula (1b) may be used as a component.
It may be contained in an amount of not more than mol%. However, equation (1a)
When the amount of the polyimide composed of the structural unit represented by the formula is less than 40 mol%, heat resistance is lowered and durability of the polyimide when wet is lowered, which is not desirable. The polyimide of the component (a) has a weight average molecular weight of 5,000 to 500,000.
Are preferred. When the weight average molecular weight is less than 5,000, thermal stability becomes poor, heat resistance decreases, and
When it is larger than 00000, the melt viscosity increases,
When used as a resin composition, workability and adhesiveness are poor.

The polyimide used in the present invention can be obtained by using a general polyimide production method. That is, for example, it can be produced from a tetracarboxylic dianhydride corresponding to each repeating structural unit and a diamine or diisocyanate corresponding to each repeating structural unit.
Specifically, 3,3 ′ as tetracarboxylic dianhydride,
It can be produced by reacting 4,4′-diphenylsulfonetetracarboxylic dianhydride with a compound represented by the formula (4) and / or a siloxane-based compound represented by the following formula (5). Q-Ar-Q (4) (wherein, Ar represents a divalent group selected from the above-mentioned structures having an aromatic ring, and Q represents an amino group or an isocyanate group.)

Embedded image (In the formula, R represents —CH ₂ OC ₆ H ₄ — in which an alkylene group having 1 to 10 carbon atoms or a methylene group is bonded to Si, and n represents an integer of 1 to 20. Q represents an amino group Or an isocyanate group.)

In the compound represented by the above formula (4),
Specific examples of the diamines in which the functional group Q is an amino group include the following. 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4 ′
-Diaminodiphenylmethane, 1,3-bis [1- (3
-Aminophenyl) -1-methylethyl] benzene,
1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,4-bis [1- (3-aminophenyl) -1-methylethyl] benzene, 1,4-bis [ 1- (4-aminophenyl) -1-methylethyl]
Benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene,
1,4-bis (4-aminophenoxy) benzene, 3,
3′-bis (3-aminophenoxy) diphenyl ether, 3,3′-bis (4-aminophenoxy) diphenyl ether, 3,4′-bis (3-aminophenoxy) diphenyl ether, 3,4′-bis (4-amino Phenoxy) diphenyl ether, 4,4′-bis (3-aminophenoxy) diphenyl ether, 4,4′-bis (4-aminophenoxy) diphenyl ether, 3,3′-bis (3-aminophenoxy) biphenyl, 3,3 ′ -Bis (4-aminophenoxy) biphenyl, 3,4'-bis (3-aminophenoxy) biphenyl, 3,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) Biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3
-Aminophenoxy) phenyl] sulfone, bis [4-
(4-aminophenoxy) phenyl] sulfone, 2,2
-Bis [3- (3-aminophenoxy) phenyl] propane, 2,2-bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane 2,2-bis [4-
(4-aminophenoxy) phenyl] propane, 2,2
-Bis [3- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) phenyl] hexafluoropropane,
2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane,
9,9-bis (3-aminophenyl) fluorene, 9,9
-Bis (4-aminophenyl) fluorene, 3,3'-diamino-2,2 ', 4,4'-tetramethyldiphenylmethane, 3,3'-diamino-2,2', 4,4'-tetraethyldiphenylmethane 3,3'-diamino-2,2 ', 4,4'
-Tetrapropyldiphenylmethane, 3,3'-diamino-2,2 ', 4,4'-tetraisopropyldiphenylmethane, 3,3'-diamino-2,2', 4,4'-tetrabutyldiphenylmethane, 3,4 '-Diamino-2,3', 4,5 '
-Tetramethyldiphenylmethane, 3,4'-diamino-
2,3 ', 4,5'-tetraethyldiphenylmethane, 3,
4'-diamino-2,3 ', 4,5'-tetrapropyldiphenylmethane, 3,4'-diamino-2,3', 4,5'-tetraisopropyldiphenylmethane, 3,4'-diamino-
2,3 ', 4,5'-tetrabutyldiphenylmethane, 4,
4'-diamino-3,3 ', 5,5'-tetramethyldiphenylmethane, 4,4'-diamino-3,3', 5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3 ' ,
5,5'-tetrapropyldiphenylmethane, 4,4'-diamino-3,3 ', 5,5'-tetraisopropyldiphenylmethane, 4,4'-diamino-3,3', 5,5'-tetrabutyldiphenylmethane 4,4'-diamino-3,3'-
Diethyl-5,5'-dimethyldiphenylmethane, 4,4 '
-Diamino-3,3'-dimethyldiphenylmethane, 4,
4'-diamino-3,3'-diethyldiphenylmethane,
4,4'-diamino-3,3 ', 5,5'-tetramethoxydiphenylmethane, 4,4'-diamino-3,3', 5,5'-
Tetraethoxydiphenylmethane, 4,4'-diamino-
3,3 ′, 5,5′-tetrapropoxydiphenylmethane,
4,4'-diamino-3,3 ', 5,5'-tetraisopropoxydiphenylmethane 4,4'-diamino-3,3', 5,
5'-tetrabutoxydiphenylmethane, 4,4'-diamino-3,3'-dimethoxydiphenylmethane, 4,4'-
And diamino-3,3'-diethoxydiphenylmethane.

In the compound represented by the formula (4), as the diisocyanates in which the functional group Q is an isocyanate group, “amino” is replaced with “isocyanate” in the diamines described above. Can be mentioned. In the compound represented by the above formula (4), diisocyanates in which the functional group Q is an isocyanate group can be easily produced by reacting the corresponding diamine exemplified above with phosgene according to a conventional method. it can.

In the siloxane compound represented by the formula (5) used as a raw material for producing polyimide, the diamines in which the functional group Q is an amino group include bis (3-aminopropyl) tetramethyldisiloxane and bis (3-aminopropyl) tetramethyldisiloxane. 10
-Aminodecamethylene) tetramethyldisiloxane, aminopropyl-terminated dimethylsiloxane tetramer, octamer, bis (3-aminophenoxymethylene) tetramethyldisiloxane, and the like, and these can be used in combination. . When tetracarboxylic dianhydride and diamine are used as raw materials, they may be used in an organic solvent in the presence of a catalyst such as tributylamine, triethylamine, or triphenyl phosphite as needed (20 parts by weight or less of the reactant). ), Heating to 100 ° C. or higher, preferably 180 ° C. or higher to directly obtain a polyimide; a polyamic acid which is a precursor of polyimide by reacting tetracarboxylic dianhydride and diamine in an organic solvent at 100 ° C. or lower Is obtained, if necessary, a dehydration catalyst such as p-toluenesulfonic acid (1 to 5 times the molar amount of tetracarboxylic dianhydride) is added, and a polyimide is obtained by imidation by heating, or Polyamic acid, acetic anhydride, propionic anhydride,
Dehydration ring closure agents such as acid anhydrides such as benzoic anhydride and carbodiimide compounds such as dicyclohexylcarbodiimide and, if necessary, ring closure catalysts such as pyridine, isoquinoline, imidazole and triethylamine (dehydration ring closure agents and ring closure catalysts are tetracarboxylic dianhydrides). (2 to 10 times the molar amount of the product) and then chemically closing the ring at a relatively low temperature (from room temperature to about 100 ° C.).

As the organic solvent used in the above reaction, N
-Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide,
Aprotic polar solvents such as 1,3-dimethyl-2-imidazolidone, phenol, cresol, xylenol,
Phenol solvents such as p-chlorophenol are exemplified. If necessary, benzene, toluene, xylene, methyl ethyl ketone, acetone, tetrahydrofuran, dioxane, monoglyme, diglyme, methyl cellosolve, cellosolve acetate, methanol, ethanol, isopropanol, methylene chloride, chloroform, trichlene, nitrobenzene, etc. Can also be used as a mixture. Further, when using tetracarboxylic dianhydride and diisocyanate as raw materials, it is possible to produce according to the method of directly obtaining the above polyimide, the reaction temperature at this time is room temperature or higher, In particular, the temperature is preferably 60 ° C. or higher. The reaction between tetracarboxylic dianhydride and diamine or diisocyanate can be carried out in an equimolar amount to obtain a polyimide having a high degree of polymerization. It is also possible to produce polyimide using an excess amount in the following range.

The bisimide compound of the above formula (2) used in the present invention may be phthalic anhydride, 4-methylphthalic anhydride, 4-ethylphthalic anhydride, 4-methoxyphthalic anhydride, 4-chlorophthalic acid. It can be produced by reacting a phthalic anhydride derivative such as anhydride, 4-bromophthalic anhydride, pyromellitic anhydride and the compound represented by the formula (4). On the other hand, the bismaleimide compound of the above formula (3) is a compound of maleic anhydride or methyl maleic anhydride, ethyl maleic anhydride,
Maleic anhydride derivatives such as 2,3-dimethylmaleic anhydride, chloromaleic anhydride, bromomaleic anhydride, 2,3-dichloromaleic anhydride and the compound represented by the above formula (4) Can be produced by reacting

The bisimide compound represented by the formula (2) used in the present invention can be more specifically produced, for example, as follows. Phthalic anhydride or a phthalic anhydride derivative in an amount of at least twice as much as the diamine in an organic solvent, if necessary, in the presence of a catalyst such as tributylamine, triethylamine, and triphenyl phosphite (2
0 parts by weight or less) and 100 ° C. or higher, preferably 180 ° C.
Heating as described above, a method for directly obtaining a bisimide, a tetracarboxylic dianhydride and a diamine are reacted at a temperature of 100 ° C. or less in an organic solvent to obtain a polyamic acid as a polyimide precursor, and if necessary, p- Dehydration catalysts such as toluenesulfonic acid (1 to 5 of phthalic anhydride or phthalic anhydride derivative)
), And imidization by heating to obtain a polyimide, or dehydration of this polyamic acid with an acid anhydride such as acetic anhydride, propionic anhydride, benzoic anhydride, or a carbodiimide compound such as dicyclohexylcarbodiimide. A ring-closing agent and, if necessary, a ring-closing catalyst such as pyridine, isoquinoline, imidazole, triethylamine, etc. (the dehydration ring-closing agent and the ring-closing catalyst are 2 to 10 moles of phthalic anhydride or a phthalic anhydride derivative), and are added at a relatively low temperature. (Room temperature to about 100 ° C.). In each case, after the completion of the ring closure reaction, the reaction solution
Pour the product into about twice as much methanol to precipitate the product,
It is possible to obtain a bisimide compound by washing and drying with methanol. Examples of the organic solvent used in the above reaction include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide, and 1,3-dimethyl-2. -Aprotic polar solvents such as imidazolidone; phenol solvents such as phenol, cresol, xylenol, and p-chlorophenol; Also, if necessary, benzene, toluene, xylene, methyl ethyl ketone, acetone, tetrahydrofuran, dioxane, monoglyme, diglyme, methyl cellosolve, cellosolve acetate, methanol, ethanol, isopropanol, methylene chloride,
It is also possible to use chloroform, trichlene, nitrobenzene, etc. in a mixture with the above solvent. Further, when phthalic anhydride or a phthalic anhydride derivative and diisocyanate are used as raw materials, it can be produced according to the above-mentioned method for directly obtaining a bisimide, and the reaction temperature at this time is room temperature. The temperature is preferably 60 ° C. or higher.

The bismaleimide compound represented by the formula (3) used in the present invention can be produced as follows. After reacting maleic anhydride or a maleic anhydride derivative and diamine in an organic solvent at a temperature of 100 ° C. or less in an organic solvent to obtain bismaleimide acid, which is a precursor of bismaleimide, twice or more moles relative to the diamine, if necessary, p- A dehydration catalyst such as toluenesulfonic acid (1 to 5 moles of maleic anhydride or a maleic anhydride derivative) was added, and the mixture was heated at 150 ° C.
A method of obtaining bismaleimide by imidization by heating to a degree, or this bismaleamide acid, acetic anhydride, propionic anhydride, acid anhydrides such as benzoic anhydride, a dehydration ring closing agent such as a carbodiimide compound such as dicyclohexylcarbodiimide and the like. If necessary, a ring-closing catalyst such as pyridine, isoquinoline, imidazole, triethylamine or the like (a dehydration ring-closing agent and a ring-closing catalyst are 2 to 10 moles of maleic anhydride or a maleic anhydride derivative) is added, and a relatively low temperature (from room temperature to room temperature). (About 100 ° C.). In any method, the imidation reaction (dehydration ring closure reaction) is preferably performed at a low temperature of 150 ° C. or less because the double bond of the maleimide group is rich in reactivity. In each case, after the completion of the ring closure reaction, the reaction solution is poured into about 10 times the amount of methanol to precipitate a product, and the product can be washed and dried with methanol to obtain a bismaleimide compound. As the organic solvent used in the above reaction, N
-Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide,
Aprotic polar solvents such as 1,3-dimethyl-2-imidazolidone, phenol, cresol, xylenol,
Phenol solvents such as p-chlorophenol are exemplified. If necessary, benzene, toluene, xylene, methyl ethyl ketone, acetone, tetrahydrofuran, dioxane, monoglyme, diglyme, methyl cellosolve, cellosolve acetate, methanol, ethanol, isopropanol, methylene chloride, chloroform, trichlene, nitrobenzene, etc. Can also be used as a mixture.

The mixing ratio of the low dielectric resin composition is such that the component (b) is 1 to 100 parts by weight based on 100 parts by weight of the component (a).
Parts by weight, preferably 10 to 80, more preferably 10 to
50. When the amount of the component (b) is less than 1 part by weight, the dielectric constant becomes high, which is not suitable for the intended use. Also, 100
If the amount is more than the weight part, when the resin composition is cured to the B stage (semi-cured), the resin composition itself becomes brittle and causes scattering of the resin. The components (a) and (b) can be mixed in a solvent in which they are dissolved. As the solvent, for example, N-methyl-2-pyrrolidone, N,
N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidone, hexane, benzene, toluene, xylene, methyl ethyl ketone, acetone, diethyl ether, tetrahydrofuran, Dioxane, 1,2-dimethoxymethane, diethylene glycol dimethyl ether, methyl cellosolve, cellosolve acetate, methanol, ethanol, propanol, isopropanol, methyl acetate,
Ethyl acetate, acetonitrile, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, dichloroethane, trichloroethane, and the like,
From these, the type and amount are appropriately selected and used so that each component is dissolved. A silane coupling agent may be added to the low dielectric resin composition.

When applied to a laminate or a metal-clad laminate, the low dielectric resin composition may contain a filler having a particle size of 1 μm or less in order to stabilize the fluidity of the resin composition. Filler content is 5% of total solids
It is in the range of -70% by weight, preferably 10-60% by weight, more preferably 20-50% by weight. When the content is lower than 5% by weight, the effect of stabilizing the fluidity decreases,
If it exceeds 70% by weight, the adhesive strength of the laminate decreases, and the dielectric constant increases. As the filler, for example, silica, quartz powder, alumina, calcium carbonate, magnesium oxide, diamond powder, mica, fluororesin, zircon powder and the like are used. The low dielectric resin composition of the present invention can have a dielectric constant in a cured state of 3.0 or less,
Also preferred. When the dielectric constant is 3.0 or less, it is possible to sufficiently cope with miniaturization of the internal circuit.

The prepreg of the present invention is obtained by filling the above-described low dielectric resin composition into a fiber reinforced material. The laminate according to the present invention has a structure in which a plurality of the prepregs are laminated. Is manufactured by applying a low dielectric resin composition varnish dissolved in the above organic solvent to a fiber reinforcement, impregnating the same, and drying. The amount of the resin composition is
It is preferable that the amount is such that the voids of the cloth can be filled after drying. The thickness of the fiber reinforcement is 0.05 to 1 mm, preferably 0.1 to 0.5 mm, more preferably 0.1 to 0.1 mm.
Set within a range of 2 mm. If the thickness is too small, the strength of the cloth is insufficient, and if it is too thick, it becomes difficult to apply and impregnate the resin composition varnish. Examples of the fiber reinforcing material include heat-resistant fibers, specifically, carbon fibers, glass fibers, aramid fibers, aromatic polyester fibers, boron fibers, silica fibers, and tetrafluorocarbon fibers. These fibers may be either long fibers or short fibers, and woven or nonwoven fabrics may be used. These reinforcing fibers may be used alone or in combination of two or more, but aramid fibers, aromatic polyester fibers or tetrafluorocarbon fibers are particularly preferred. The prepreg or laminate prepared by applying a resin composition varnish to a cloth and impregnating the cloth may be one whose surface is smoothed using a heat laminator, a calendar or the like.

The metal-clad laminate of the present invention is obtained by further forming a metal layer made of a metal foil or a metal plate on one or both sides of the above-described prepreg or laminate. In order to produce such a metal-clad laminate, a press machine, a vacuum press machine or a heat laminator, etc., on one or both surfaces of the prepreg or laminate filled with the resin composition using a resin composition,
What is necessary is just to laminate | stack and integrate a metal foil or a metal plate. 5μm ~ 200μm thick as metal foil or metal plate
Copper, white copper, silver, iron, 42 alloy, and stainless steel can be used.

On one or both surfaces of the above-mentioned prepreg or laminated plate, or on the surface of the metal-clad laminated resin composition,
A peelable protective film may be provided. Examples of the protective film include a polypropylene film, a fluororesin-based film, a polyethylene film, a polyethylene terephthalate film, paper, and, in some cases, those obtained by imparting a release property with a silicone resin. These peelable films have a 90 ° peel strength of 0.01 to 7.0.
It is desirably in the range of 0 g / cm. When the peel strength is less than 0.01 g / cm, there is a problem that the peelable film is easily peeled when the laminate or the like and the single-sided metal-clad laminate are transported. The functional film does not peel off cleanly from the laminate or the like and the one-sided metal-clad laminate, and the workability is deteriorated.

[0022]

EXAMPLES [Synthesis Example of Polyimide] [Synthesis Example 1] 1,4-bis was added to a flask equipped with a stirrer.
19.58 g of (4-aminophenoxy) benzene (67
Mmol) and 1,3-bis (3-aminopropyl) -1,
8.20 g of 1,3,3-tetramethyldisiloxane (33
Mmol) and 3,3 ', 4,4'-diphenylsulfonate
35.83 g (100 mmol) of lacarboxylic dianhydride
And N-methyl-2-pyrrolidone (hereinafter referred to as “NMP”)
You. ) Introduce 300 ml under ice temperature and continue stirring for 1 hour
I did. Next, the solution was reacted at room temperature for 2 hours,
Mido acid was synthesized. 50 ml of the obtained polyamic acid
Toluene and 1.0 g of p-toluenesulfonic acid were added,
Heat to 160 ° C and azeotrope with toluene as the reaction progresses
The imidation reaction was performed for 3 hours while separating the
Was. Thereafter, toluene was distilled off, and the resulting polyimide resin was removed.
Pour the varnish into methanol, separate the resulting precipitate,
Through the steps of crushing, washing and drying, the above formula
(1a) and (1b) have a molar ratio of each structural unit of (1).
a): Polyimide 5 represented by (1b) = 67: 33
8.0 g (97% yield) were obtained. Of the resulting polyimide
When the infrared absorption spectrum was measured, it was 1718 cm^-1
And 1783 cm^-1Typical imide absorption
Was.

[Synthesis Example 2] 1,3-bis (4-aminophen)
Enoxy) benzene 19.58 g (67 mmol) and 1,1
3-bis (3-aminopropyl) -1,1,3,3, -tetra
8.20 g (33 mmol) of lamethyldisiloxane and 3,
3 ', 4,4'-diphenylsulfonetetracarboxylic acid
35.83 g (100 mmol) of water and NMP300
ml of each structural unit in the same manner as in Synthesis Example 1
The molar ratio is (1a) :( 1b) = 67: 33.
58.0 g (97% yield) of the imide was obtained. The obtained po
When the infrared absorption spectrum of the imide was measured, 17
18cm^-1 And 1783 cm^-1Typical imide absorption
Was observed. [Synthesis Example 3] 1,3-bis [1- (4-aminopheni)
23) g (67)
Mmol) and 1,3-bis (3-aminopropyl) -1,
8.20 g of 1,3,3-tetramethyldisiloxane (33
Mmol) and 3,3 ', 4,4'-diphenylsulfonate
35.83 g (100 mmol) of lacarboxylic dianhydride
And the same method as in Synthesis Example 1 using 300 ml of NMP
And the molar ratio of each structural unit is (1a) :( 1b) = 67:
62.5 g (98% yield) of the polyimide represented by 33
Obtained. Measure the infrared absorption spectrum of the obtained polyimide
1718cm^-1 And 1783 cm^-1Typical
Typical imide absorption was observed.

[Synthesis Example 4] 4,4'-bis (4-aminophen)
Enoxy) biphenyl 24.68 g (67 mmol)
1,3-bis (3-aminopropyl) -1,1,3,3,-
8.20 g (33 mmol) of tetramethyldisiloxane
And 3,3 ', 4,4'-diphenylsulfonetetracarboxylic
35.83 g (100 mmol) of acid dianhydride and NMP
Each composition was prepared in the same manner as in Synthesis Example 1 using 300 ml.
The molar ratio of the units is (1a) :( 1b) = 67: 33.
64.0 g (yield 98%) of the resulting polyimide was obtained. Get
Measurement of the infrared absorption spectrum of the polyimide
Ro, 1718cm^-1 And 1783 cm^-1Typical immi
The absorption of cadmium was observed. [Synthesis Example 5] Bis [(4-aminophenoxy) pheni
L] ether 25.75 g (67 mmol) and 1,3-bi
(3-aminopropyl) -1,1,3,3, -tetramethyl
8.20 g (33 mmol) of rudisiloxane and 3,3 ′,
4,4'-diphenylsulfonetetracarboxylic dianhydride
35.83 g (100 mmol) and 300 ml of NMP
And in the same manner as in Synthesis Example 1,
Poly (R) having a ratio of (1a) :( 1b) = 67: 33
64.0 g of the amide (97% yield) were obtained. The resulting poly
When the infrared absorption spectrum of the amide was measured, 1718
cm^-1 And 1783 cm^-1Typical imide absorption
Was called.

[Synthesis Example 6] Bis [4- (4-aminophen)
Noxy) phenyl] sulfone 28.98 g (67 mmol
) And 1,3-bis (3-aminopropyl) -1,1,3,
8.20 g of 3, -tetramethyldisiloxane (33 mmol
) And 3,3 ', 4,4'-diphenylsulfonetetracar
35.83 g (100 mmol) of boronic dianhydride and N
Using 300 ml of MP, in the same manner as in Synthesis Example 1,
When the molar ratio of the structural units is (1a) :( 1b) = 67: 33
65.0 g (yield 94%) of the indicated polyimide was obtained.
When the infrared absorption spectrum of the obtained polyimide was measured
Roller, 1718cm^-1 And 1783 cm^-1A typical
Mid absorption was observed. [Synthesis Example 7] 2,2-bis [4- (4-aminophenoxy)
Cis) phenyl] propane 27.50 g (67 mmol)
And 1,3-bis (3-aminopropyl) -1,1,3,3,
-8.20 g of tetramethyldisiloxane (33 mmol
) And 3,3 ', 4,4'-diphenylsulfonetetracar
35.83 g (100 mmol) of boric acid dianhydride and N
Using 300 ml of MP, in the same manner as in Synthesis Example 1,
When the molar ratio of the structural units is (1a) :( 1b) = 67: 33
65.0 g (yield 96%) of the indicated polyimide were obtained.
When the infrared absorption spectrum of the obtained polyimide was measured
Roller, 1718cm^-1 And 1783 cm^-1A typical
Mid absorption was observed.

Synthesis Example 8 2,2-Bis [4- (4-A
Minophenoxy) phenyl] hexafluoropropane 3
4.74 g (67 mmol) and 1,3-bis (3-amino
Propyl) -1,1,3,3-tetramethyldisiloxane
8.20 g (33 mmol) and 3,3 ', 4,4'-diphenyi
35.83 g of sulfonetetracarboxylic dianhydride (1
(00 mmol) and 300 ml of NMP
In the same manner as in 1, the molar ratio of each structural unit is (1a):
(1b) = 74.0 g of polyimide represented by 67:33
(98% yield). Infrared absorption of the obtained polyimide
When the spectrum was measured, 1718 cm^-1 And 17
83cm^-1A typical imide absorption was observed. [Synthesis Example 9] 9,9-bis (4-aminophenoxy) phenyl
23.35 g (67 mmol) of fluorene and 1,3-bis
(3-aminopropyl) -1,1,3,3, -tetramethyl
8.20 g (33 mmol) of disiloxane and 3,3 ', 4,
4'-diphenylsulfonetetracarboxylic dianhydride 3
5.83 g (100 mmol) and 300 ml of NMP
And the molar ratio of each structural unit in the same manner as in Synthesis Example 1.
Is a polyimid represented by (1a) :( 1b) = 67: 33
60.5 g (95% yield) were obtained. Polyimi obtained
When the infrared absorption spectrum of
m^-1 And 1783 cm^-1Typical imide absorption
Was done.

Synthesis Example 10 2,2-Bis [4- (4-
Aminophenoxy) phenyl] propane 20.53 g
(50 mmol) and 1,3-bis (3-aminopropyl
) -1,1,3,3-tetramethyldisiloxane 12.
43 g (50 mmol) and 3,3 ', 4,4'-diphenyl
35.83 g of sulfonetetracarboxylic dianhydride (10
0 mmol) and 300 ml of NMP.
In the same manner as described above, the molar ratio of each structural unit is (1a) :( 1
b) 61.0 g of polyimide represented by = 50: 50 (yield
93%). Infrared absorption spectrum of the obtained polyimide
When the spectrum was measured, 1718 cm^-1And 178
3cm^-1A typical imide absorption was observed. [Synthesis Example 11] 2,2-bis [4- (4-aminopheno)
Xy) phenyl] propane 30.79 g (75 mM
) And 1,3-bis (3-aminopropyl) -1,1,3,
6.21 g of 3, -tetramethyldisiloxane (25 mmol
) And 3,3 ', 4,4'-diphenylsulfonetetracar
35.83 g (100 mmol) of boric acid dianhydride and N
Using 300 ml of MP, in the same manner as in Synthesis Example 1,
When the molar ratio of the structural units is (1a) :( 1b) = 75: 25
65.0 g (yield 94%) of the indicated polyimide was obtained.
When the infrared absorption spectrum of the obtained polyimide was measured
Roller, 1718cm^-1 And 1783 cm^-1A typical
Mid absorption was observed.

[Synthesis Example 12] 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane 32.84 g
(80 mmol) and 1,3-bis (3-aminopropyl
) -1,1,3,3-tetramethyldisiloxane 4.9
7 g (20 mmol) and 3,3 ', 4,4'-diphenyls
35.83 g of rufonetetracarboxylic dianhydride (100
Mmol) and 300 ml of NMP,
In a similar manner, the molar ratio of each structural unit is (1a) :( 1
b) 68.0 g of polyimide represented by = 80: 20 (yield
97%). Infrared absorption spectrum of the obtained polyimide
It was 1718cm^-1 And 1783
cm^-1A typical imide absorption was observed. [Synthesis Example 13] 2,2-bis [4- (4-aminopheno)
Xy) phenyl] propane 30.79 g (75 mM
) And 1,3-bis [(aminophenoxy) methyl]-
9.42 g of 1,1,3,3-tetramethyldisiloxane
(25 mmol) and 3,3 ', 4,4'-diphenylsulfo
35.83 g of tetracarboxylic dianhydride (100 mm
Mol) and 300 ml of NMP, as in Synthesis Example 1.
And the molar ratio of each structural unit is (1a) :( 1b) = 7
69.0 g of a polyimide represented by 5:25 (yield 95
%). When the infrared absorption spectrum was measured,
720,1783cm^-1Typical imide absorption
Was done.

[Synthesis Example 14] 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane 30.79 g
(75 mmol) and an aminopropyl-terminated dimethylsiloxane tetramer represented by the following general formula (5) (Q = N
Using 10.72 g (25 mmol) of H ₂ , R = propylene, n = 3), 35.83 g (100 mmol) of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and 300 ml of NMP By the same method as in Synthesis Example 1, the molar ratio of each structural unit was (1a) :( 1b) = 75: 25.
67.0 g (yield: 91%) of a polyimide represented by the following formula: was obtained. When the infrared absorption spectrum was measured, 1712,
A typical imide absorption was observed at 1783 cm ^-1 .

[0030]

Embedded image

Synthesis Example 15 4,4′-Diamino-3,
7.76 g of 3 ', 5,5'-tetraethyldiphenylmethane
(25 mmol), 6.21 g (25 mmol) of bis (3-aminopropyl) tetramethyldisiloxane and 3,3
17.91 g (50 mmol) of 3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride and 150 m of NMP
Using 1 in the same manner as in Synthesis Example 1, 27.4 g (yield: 91%) of a polyimide having a molar ratio of each structural unit of (1a) :( 1b) = 50: 50 was obtained. When the infrared absorption spectrum was measured, typical imide absorptions were observed at 1720 and 1780 cm ^-1 . Synthesis Example 16 11.4 g (37.5 mmol) of 4,4'-diamino-3,3 ', 5,5'-tetraethyldiphenylmethane and 3.11 g of bis (3-aminopropyl) tetramethyldisiloxane (12 0.5 mmol) and 3,3 ', 4,
4'-diphenylsulfonetetracarboxylic dianhydride 1
Using 7.91 g (50 mmol) and 150 ml of NMP, 29.6 g (yield: 92) of a polyimide having a molar ratio of each structural unit represented by (1a) :( 1b) = 75: 25 in the same manner as in Synthesis Example 1. %). When the infrared absorption spectrum was measured, typical imide absorptions were observed at 1720 and 1780 cm ^-1 .

[Synthesis Example 17] 2,2-bis [4- (4-A
Minophenoxy) phenyl] propane 29.42 g (72
Mmol) and in the above formula (5), Q = NH_Two, R = P
Ropyr, dimethylsiloxane 21.7 represented by n = 7
5 g (28 mmol) and 3,3 ', 4,4'-diphenyls
35.83 g of rufonetetracarboxylic dianhydride (100
Mmol) and 300 ml of NMP,
In a similar manner, the molar ratio of each structural unit is (1a) :( 1
b) = 78.4 g of polyimide represented by 72:28 (yield
94%). Infrared absorption spectrum of the obtained polyimide
It was 1718cm^-1 And 1783
cm^-1A typical imide absorption was observed.

[Synthesis Example of Bisimide Compound] [Synthesis Example 18] 4,4′-
Bis (3-aminophenoxy) biphenyl 36.8 g
(100 mmol) and 31.1 g of phthalic anhydride (210
Mmol) and 500 ml of NMP at an ice temperature.
Stirring was continued for hours. Next, this solution was reacted at room temperature for 2 hours to synthesize amic acid. 40.4 g (400 mmol) of triethylamine and acetic anhydride 3 were added to the obtained amic acid.
0.6 g (300 mmol) was slowly added dropwise and stirring was continued at room temperature for 2 hours. The solution obtained is poured into methanol and the precipitate is filtered. This precipitate was washed with methanol and dried at 150 ° C. for 2 hours to obtain 47.5 g (yield based on diamine: 76%) of the bisimide compound represented by the above formula (2). It was measured infrared absorption spectrum, the absorption of typical imides 1720,1780Cm ^-1 is absorption of ether was observed at 1240 cm ^-1. [Synthesis Example 19] 41.1 g (100 mmol) of 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 31.1 g (210 mmol) of phthalic anhydride and N
Using 500 ml of MP and 5 in the same manner as in Synthesis Example 18
3.5 g (80% yield based on diamine) of the bisimide compound represented by the above formula (2) was obtained. When the infrared absorption spectrum was measured, it was 1720, 1780 cm
^-1 and typical ether absorption at 1240 cm ^-1 .

Synthesis Example 20 34.4 g of 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene (10
0 mmol), 31.1 g (210 mmol) of phthalic anhydride and 500 ml of NMP in the same manner as in Synthesis Example 18 to obtain 58.0 g (96% yield based on diamine) of the bisimide represented by the above formula (2). A system compound was obtained. When the infrared absorption spectrum was measured, 1720, 1780
Typical imide absorption was observed at cm ^-1 . [Synthesis Example 21] 36.8 g (100 mmol) of 4,4'-bis (4-aminophenoxy) biphenyl, 31.1 g (210 mmol) of phthalic anhydride, and 500 m of NMP
Using l, 56.5 g (90% yield based on diamine) of the bisimide compound represented by the above formula (2) was obtained in the same manner as in Synthesis Example 18. It was measured infrared absorption spectrum, the absorption of typical imides 1720,1780Cm ^-1 is absorption of ether was observed at 1240 cm ^-1.

[Synthesis Example 22] 2,2-bis (4- (4-
Aminophenoxy) phenyl) propane 41.1 g (1
(00 mmol), 31.1 g (210 mmol) of phthalic anhydride and 500 ml of NMP, in the same manner as in Synthesis Example 18, 62.3 g (93% yield based on diamine) of the bisimide represented by the above formula (2) A system compound was obtained. When the infrared absorption spectrum was measured, 1720, 178
Typical absorption of imide to 0 cm ^-1 is absorption of ether was observed at 1240 cm ^-1. Synthesis Example 23 31.0 g (100 mmol) of 4,4′-diamino-3,3 ′, 5,5′-tetraethyldiphenylmethane, 31.1 g (210 mmol) of phthalic anhydride and N
Using 500 ml of MP and 4 in the same manner as in Synthesis Example 18
7.4 g (83% yield based on diamine) of the bisimide compound represented by the above formula (2) was obtained. When the infrared absorption spectrum was measured, it was 1720, 1780 cm
^{At -1} , typical imide absorption was observed.

[Synthesis Example 24] As in Synthesis Example 18, using 43.2 g (100 mmol) of bis (4- (3-aminophenoxy) phenyl) sulfone, 31.1 g (210 mmol) of phthalic anhydride and 500 ml of NMP. By the method described above, 59.6 g (yield based on diamine: 86%) of the bisimide compound represented by the above formula (2) was obtained. When the infrared absorption spectrum was measured, it was 1720, 1780 cm
^-1 and typical ether absorption at 1240 cm ^-1 .

Synthesis Example 25 A bisimide compound satisfying the above formula (3) and having the following chemical formula ("BMI-80"
I Kasei Co., Ltd.).

Embedded image

[Resin Composition Examples] 100 parts by weight of the polyimide resin obtained in Synthesis Examples 1 to 17 and Synthesis Examples 18 to 25
Was added to tetrahydrofuran, sufficiently mixed and dissolved to obtain varnishes comprising various low dielectric resin compositions shown in Table 1. The silica filler of Resin Composition Example 27 had an average particle diameter of 0.07.
μm (Arakawa Chemical).

[0039]

[Table 1]

Examples 1-27 Resin Composition Examples 1
The resin composition varnish obtained in 27 was impregnated with 100 parts by weight of an aromatic polyester nonwoven fabric (0.1 mm in thickness, manufactured by Kuraray Co., Ltd.) to 120 parts by weight of the resin composition at a solid content to obtain 14
The prepreg was dried in a drying path at 0 ° C. for 5 minutes. The obtained prepreg was tack-free, flexible, and excellent in workability. Four prepregs were stacked, 18 μm copper foil was further disposed on the upper and lower outermost layers, and the mixture was molded under a pressure of 20 kg / cm ² at 200 ° C. for 1 hour to form a 0.4 mm double-sided copper clad. A laminate was obtained.
The obtained laminate was tested for dielectric constant, peel strength, solder heat resistance, and PCBT. Table 2 shows the test results. Example 28 A 0.4 mm double-sided copper-clad laminate was obtained in the same manner as in Example 1, except that the aromatic polyester nonwoven fabric was replaced with an aramid nonwoven fabric (0.1 mm in thickness, manufactured by DuPont). Table 2 shows the test results of the obtained laminate. [Example 29] The same procedure as in Example 1 was repeated, except that the aromatic polyester nonwoven fabric was replaced with a tetrafluorocarbon nonwoven fabric (0.1 mm in thickness, manufactured by Hamakawa Paper Mills).
mm double-sided copper-clad laminate was obtained. Table 2 shows the test results of the obtained laminate. [Example 30] A copper foil having a thickness of 18 µm was replaced with a copper foil having a thickness of 18 µm.
The same operation as in Example 1 was repeated except that the alloy foil was replaced with two alloy foils.
A 4-mm double-sided copper-clad laminate was obtained. Table 2 shows the test results of the obtained laminate.

Comparative Example 1 A 0.4 mm double-sided copper-clad laminate was obtained in the same manner as in Example 1 except that "Lark TPI" manufactured by Mitsui Toatsu Chemicals was used as the resin composition. Table 2 shows the test results of the obtained laminate.

[Evaluation Method] [Dielectric constant] The capacitance was measured at a frequency of 1 MHz in accordance with JIS C6481 (relative dielectric constant and dielectric loss tangent). [Peel strength] JIS C6481 (peeling strength)
It measured according to. [Solder heat resistance] JIS C6481 (Solder heat resistance)
The measurement was carried out according to the above-mentioned method, and the presence or absence of abnormal appearance at 260 ° C. was examined. [PCBT (Pressure Cooker Biasd Test)] A pattern having a line interval of 100 μm is formed on the surface of the laminate by etching, a prepreg having a thickness of 0.1 mm is laminated on the pattern, a pressure of 20 kg / cm ² and a temperature of 200 ° C. For 2 hours to prepare a test body. Under the conditions of 5 V applied, 121 ° C., 2 atm, and 100% RH, the existence of a short circuit between the patterns was examined.

[0043]

[Table 2]

[0044]

Industrial Applicability The resin composition of the present invention has a low dielectric constant and excellent heat resistance, and a prepreg, a laminate, and the like using the resin composition.
Since the metal-clad laminate has a low dielectric constant, excellent heat resistance, and sufficient peel strength at room temperature, it can be suitably used as a circuit laminate such as a printed wiring board.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AB33B AB33C AK49A AL05A BA03 BA06 BA10B BA10C DG11A DG15A DH01A GB43 JG05 4J002 BD122 BD153 CF163 CL063 CM041 CN031 CP171 DA016 DA017 DA116 DE076 DE146 DE236 DJ016 DJ017 DJ0400 DK FA GQ00 HA05 5G305 AA06 AA12 AB10 AB24 AB34 AB36 BA09 BA23 BA25 BA26 CA03 CA11 CA20 CA21 CA26 CA38 CC01 CC02 CC13 CD01 CD02

Claims (9)

[Claims] 1. Component (a): represented by the following formula (1a)
100 to 40 mol% of at least one structural unit
At least one of the structural units represented by the formula (1b) is 0
At least one polyimide consisting of at least 60 mol%
And Component (b): a compound represented by the following formula (2) or (3)
Characterized by having at least one kind selected from objects
Low dielectric resin composition. Embedded image(In the formula (1a), Ar represents the following structure having an aromatic ring:
Shows the divalent group selected. In the formula (1b), R represents 1 carbon atom
10 to 10 alkylene or methylene groups are bonded to Si
-CH_TwoOC₆H_FourRepresents-and n is an integer of 1 to 20
Means )(Where R¹, R^Two, R^ThreeAnd R^FourAre the same but different
A hydrogen atom, an alkyl group having 1 to 4 carbon atoms
Or an alkoxy group, but all these groups are
They cannot be elementary atoms. )(Wherein, Ar is selected from the above structures having an aromatic ring
Represents a divalent group;^Five , R⁶And R⁷Are the same
May be different, hydrogen, chlorine, bromine,
Carboxyl group, alkyl group having 1 to 4 carbon atoms or alcohol
Shows a xy group. ) 2. The low dielectric resin composition according to claim 1, wherein a filler having a particle size of 1 μm or less is contained in an amount of 5 to 70% by weight of the total solid. 3. Component (a) (100 parts by weight)
The low dielectric resin composition according to claim 1, wherein the component (b) is mixed in an amount of 1 to 100 parts by weight. 4. The low dielectric resin composition according to claim 1, wherein the dielectric constant in a cured state is 3.0 or less. 5. A prepreg comprising the low dielectric resin composition according to claim 1 and a fiber reinforcing material. 6. A laminate comprising a plurality of the prepregs according to claim 5 laminated. 7. A metal-clad laminate, wherein a metal layer is formed on one or both sides of the prepreg according to claim 5 or the laminate according to claim 6. 8. The prepreg according to claim 5, wherein the fiber reinforcing material is a woven or non-woven fabric made of fibers selected from aramid fibers, aromatic polyester fibers, and tetrafluorocarbon fibers. 9. The method according to claim 9, wherein the metal layer is made of copper, copper, silver, iron,
The metal-clad laminate according to claim 7, comprising at least one selected from an alloy and stainless steel.