JP2006274218A - Resin composition, resin layer and carrier material and circuit board each having resin layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in electric properties and capable of forming fine via holes by laser when formed as a resin layer of the circuit board and to provide a resin layer excellent in electric properties and capable of forming fine via holes by laser and a carrier material and a circuit board each equipped with resin layer using the same. <P>SOLUTION: The resin composition constitutes an insulating layer of a circuit board forming via holes by laser irradiation and the composition comprises a cyclic olefin resin having polymerizable functional groups on the side chains, an azide derivative as a laser processing property-imparting agent and a polymerization initiator. The resin layer is constituted of the resin composition. The carrier material having the resin layer forms the resin layer on at least one surface of the carrier material. The circuit board has the resin layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin composition, a resin layer, a carrier material with a resin layer, and a circuit board.

  With the recent increase in the density of multilayer wiring boards and the increase in the speed of electrical signals, not only the density of wiring circuits and the diameter of vias but also the required characteristics for insulating resins are becoming increasingly severe. In particular, the requirements regarding electrical characteristics are severe, and the limit is beginning to appear in the conventional insulating resin composed of an epoxy resin system having low cost and high handling properties. Therefore, polyimide resins that are excellent in electrical characteristics, reliability, and heat resistance are actively used in the latest multilayer wiring boards. In such a high heat-resistant polyimide resin, a high temperature process is required at the time of ring closure from polyamic acid, which is a resin precursor, and the resin is very excellent in heat resistance. There is a problem that it is very bad and the cost is high. On the other hand, when a solvent-soluble polyimide resin having excellent processability is used, there is a problem that heat resistance and reliability are poor. Therefore, techniques such as blending a thermosetting resin with a solvent-soluble polyimide resin are taken.

  In addition, in a semiconductor package substrate on which a semiconductor is directly mounted, warpage and thermal stress due to the difference in thermal expansion coefficient between the semiconductor and the semiconductor package substrate become a problem, so the resin used for the semiconductor package substrate has electrical characteristics. In addition, it is important that the thermal expansion coefficient of the insulating resin is small. In this case, for example, when the thickness of the insulating resin layer in the semiconductor package substrate is 100 μm or more, low thermal expansion has been achieved by forming the insulating resin layer by impregnating the glass resin with the insulating resin. In this semiconductor package substrate, the thickness of the insulating resin layer is as thin as 50 μm or less, and a glass cloth cannot be used. Therefore, a method of blending an inorganic filler for reducing the thermal expansion has been taken. The inorganic filler is mixed into the resin composition using a three roll, homogenizer, ball mill, three-one motor, rotation / revolution mixer, vacuum / revolution / revolution mixer, etc. It is technically difficult to completely impregnate and disperse the resin. In particular, when the average particle size of the inorganic filler is 1 μm or less, the specific surface area per unit weight is large, and the interaction between the inorganic fillers is large. Therefore, it is technically difficult to completely disperse the inorganic filler in the resin without aggregation.

  By filling the insulating resin with the inorganic filler in this way, a low thermal expansion can be achieved to some extent, but as the insulating resin layer in the semiconductor package substrate becomes thinner, the filling of the inorganic filler from the viewpoint of insulation reliability and workability The rate will be limited. Therefore, in order to achieve lower thermal expansion, it is necessary to lower the thermal expansion coefficient of the insulating resin itself.

  On the other hand, from the viewpoint of controlling the impedance of the semiconductor package substrate, it is also important to control the thickness of the insulating resin layer. In the method of directly applying the insulating resin to the package substrate, it is difficult to control the film thickness. Therefore, a dry film type in which an insulating resin layer is previously formed on a copper foil or PET is suitable for the film thickness control. The characteristics required for the insulating resin of the dry film have sufficient film properties, and low temperature processability and film storage stability are important from the viewpoint of productivity. Therefore, there is a demand for an insulating resin that is a dry film type insulating resin and that satisfies all characteristics such as electrical characteristics, a low expansion coefficient, and workability.

Examples of thermosetting resins that satisfy these characteristics include cyanate resins. In order to completely cure the cyanate resin, for example, high-temperature heat treatment at 250 ° C. for 3 hours is required. (For example, see Non-Patent Document 1.) However, when curing is performed at a high temperature of 250 ° C., stress is accumulated in the resin layer when the temperature is returned to room temperature after curing, and peeling or the like occurs at the interface with a metal layer such as copper. It can happen. In addition, when the curing process is performed at a temperature lower than the above temperature, unreacted cyanate resin remains, which may cause voids in the resin layer, resulting in a problem in reliability. Another problem is that the triazine ring formed by heat-curing the cyanate resin is easily hydrolyzed by water absorption.
In addition, since the cyanate resin itself is brittle, a method of mixing with an epoxy resin, a polyimide resin, or the like has been studied in order to improve them (for example, see Patent Documents 1 and 2). However, heating at 150 ° C. to 300 ° C. is required during curing. However, as described above, heat curing at high temperature may cause stress in the resin layer, and heat reaction at low temperature may leave unreacted cyanate resin.
I. Hamerton. CHEMISTRY AND TECHNOLOGY OF Cyanate ESTER RESINS: BLACKIE ACADEMIC & PROFESSIONAL 164 (1994) Japanese Patent Laid-Open No. 5-140526 JP-A-5-32950

The present invention has been made in view of such current problems, and in the case of a resin layer, the resin composition has low thermal expansion and is excellent in electrical characteristics, workability, storage stability and reliability. Is to provide.
Another object of the present invention is to provide a resin layer having low thermal expansion and excellent reliability.
Another object of the present invention is to provide a carrier material with a resin layer having low thermal expansion and excellent reliability.
Another object of the present invention is to provide a circuit board having low thermal expansion and excellent reliability.

That is, the above-mentioned problems can be solved by the present invention of the items (1) to (15).
(1) A resin composition comprising a cyanate resin (A), a solvent-soluble polyimide resin (B), a solvent-soluble epoxy resin (C), and an acid anhydride (D).
(2) The cyanate resin (A) is trimerized when the cyanate compound represented by the general formula (1), the cyanate compound represented by the general formula (2), and the cyanate group of these compounds are 40% or less. The resin composition according to item (1), which is at least one cyanate compound selected from among cyanate compounds having at least two cyanate groups.

(In Formula (1), R < ₁ > -R < ₆ > shows either a hydrogen atom, a methyl group, a fluoroalkyl group, and a halogen atom each independently.)

(In the formula _(2), R 1 to R ₃ are each independently a hydrogen atom, one of methyl group, a fluoroalkyl group and a halogen atom, n is an integer from 0 to 6.)

(3) The resin composition according to item (1) or (2), wherein the solvent-soluble polyimide resin (B) is a polyimidesiloxane resin.
(4) The polyimidesiloxane resin contains 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 4,4′- At least one aromatic tetracarboxylic acid component selected from oxydiphthalic dianhydride and 4,4′-diphenylsulfonetetracarboxylic dianhydride, and diaminopolysiloxane 10 represented by the general formula (3): The resin composition according to item (3), which is synthesized by reacting a diamine component comprising 80 mol% and aromatic diamine 20 to 90 mol%.

(In the formula (3), _{R 7} represents a hydrocarbon _group, R 8 _{to R 11} represents an alkyl group or a phenyl group having 1 to 10 carbon atoms, n is an integer from 1 to 20.)

(5) The resin composition according to any one of (1) to (4), wherein the solvent-soluble epoxy resin (C) is an aralkyl-modified epoxy resin.
(6) The resin composition according to any one of Items (1) to (5), wherein the acid anhydride (D) is maleic anhydride.
(7) The resin composition according to any one of (1) to (6), wherein the resin composition includes a cyanurate resin (E).
(8) The resin composition according to any one of (1) to (7), wherein the resin composition includes an inorganic filler (F).
(9) The resin composition according to item (8), wherein the inorganic filler (F) is silica.
(10) The resin composition according to (8) or (9), wherein the inorganic filler (F) has an average particle size of 1 μm or less.
(11) The resin according to any one of (8) to (10), wherein the inorganic filler (F) is the polyimide resin dispersed in advance in a soluble solvent (G). Composition.
(12) The resin composition according to item (11), wherein the solvent (G) soluble in the polyimide resin and the epoxy resin is N-methyl-2-pyrrolidone.
(13) The resin composition according to any one of items (1) to (12), further comprising an imidazole catalyst (H).
(14) A resin layer comprising the resin composition according to any one of items (1) to (13).
(15) A carrier material with a resin layer, wherein the resin layer according to item (14) is formed on at least one surface of the carrier material.
(16) A circuit board comprising the resin layer according to item (14).

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which is excellent in an electrical property, workability, a preservability, and reliability with low thermal expansion can be provided.
Another object of the present invention is to provide a resin layer having low thermal expansion and excellent reliability.
Another object of the present invention is to provide a carrier material with a resin layer having low thermal expansion and excellent reliability.
Another object of the present invention is to provide a circuit board having low thermal expansion and excellent reliability.

  Hereinafter, the resin composition, resin layer, carrier material with a resin layer, and circuit board of the present invention will be described.

By using a cyanate resin in the resin composition of the present invention, the processability at a low temperature, for example, at the time of embedding a circuit in the resin layer obtained from the resin composition of the present invention in the production of a circuit board, 100 The circuit can be embedded by heating at a low temperature of about 150 ° C. to 150 ° C., and when the resin composition is cured to form a resin layer, the heat elastic reliability is high at a high temperature exceeding 200 ° C. with a high elastic modulus when heated. And having a low coefficient of thermal expansion, a low dielectric constant, and a low dielectric loss tangent can be obtained.
As such a cyanate resin, at least two compounds represented by the general formula (1), the compound represented by the general formula (2), and the cyanate group of these compounds trimerized at 40% or less. Cyanate compounds having the above cyanate groups are preferred. Specifically, as represented by the general formula (1), bisphenol M cyanate ester, dicyclopentadienyl bisphenol cyanate ester, bisphenol A cyanate ester, tetramethylbisphenol F cyanate ester, bisphenol E cyanate ester, hexa Examples thereof include fluorobisphenol A cyanate ester and bisphenol C cyanate ester. Examples of those represented by the general formula (2) include phenol novolak cyanate ester and compounds obtained by trimerizing these cyanate groups within the above range. . Of these, phenol novolac polycyanate and cresol novolac polycyanate are particularly preferable. Among these, at least one kind or two or more kinds are used.

The solvent-soluble polyimide resin (B) used in the present invention is not limited as long as it is a polyimide resin soluble in a solvent. The polyimide resin will be described later as a soluble solvent. The polyimide resin further includes resins having an imide group such as polyetherimide resin, polyamideimide resin, and polyesterimide resin. Among these, a resin obtained by reacting an aromatic tetracarboxylic acid component and a diamine component to polymerize and imidize is preferable.
Examples of the aromatic tetracarboxylic acid component include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, Examples include 4'-oxydiphthalic dianhydride and 4,4'-diphenylsulfone tetracarboxylic dianhydride. One or more aromatic tetracarboxylic acids selected from these can be used.
Examples of the diamine component include p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,5- Diamino-p-xylene, 2,5-diamino-m-xylene, 2,5-diaminopyridine, 2,6-diaminopyridine, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3 ′ -Diaminodiphenylpropane, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylhexafluoropropane, 4,4'-diaminodiphenylhexafluoropropane, 3,3'-diaminodiphenyl ether, 4,4'-diamino Diphenyl ether, 3,4'-diaminodiphenyl ether, benzi 3,3′-diaminobiphenyl, 3,3′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 4,4 ′ -Diaminobenzanilide, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6-xylidine, 4,4'-methylenedi-2,6-diethylaniline, 3,3'-dimethyl- 4,4′-diaminobiphenyl, 3,3′-dimethoxybenzidine, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4- Aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) Enyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, bis [ 4- (4-aminophenoxy) phenyl] ether, 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8 -Diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 1,4-diaminocyclohexane, 1,2-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, bis (4 -Amino-3-methylcyclohexyl) methane, 2,5-dimethylhexamethylene Amine, 2,5-dimethyl heptamethylene diamine, 3-methyl heptamethylene diamine, 4,4-dimethyl-heptamethylene diamine, include 5-methyl nonamethylenediamine. It is preferable to use one or more diamines selected from these.
By using a solvent-soluble polyimide resin, when it is used as a resin layer, it is possible to obtain a resin composition that is excellent in sheet properties in an uncured state and excellent in film strength and flexibility of a cured product.

  The solvent-soluble polyimide resin used in the present invention is more preferably a polyimide siloxane resin comprising an aromatic tetracarboxylic acid and a diamine and diaminopolysiloxane. By including siloxane in the polyimide resin, the flexibility and embeddability of the film are improved. Examples of the polyimidesiloxane resin include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and 4,4′-oxydiphthalic acid. At least one aromatic tetracarboxylic acid component selected from dianhydride and 4,4′-diphenylsulfonetetracarboxylic dianhydride, and diaminopolysiloxane 10-80 represented by the general formula (3) It is preferably a high molecular weight polyimide siloxane resin obtained by reacting with a diamine component comprising 20% by mole and 20% to 90% by mole of an aromatic diamine, followed by polymerization and imidization. The weight average molecular weight of such a polyimidesiloxane resin is preferably 30,000 to 100,000, more preferably 40000 to 80,000. By using a high molecular weight polyimide siloxane resin, the flexibility of the film is improved.

The diaminopolysiloxane represented by the general formula (3) has a hydrocarbon group as R _{7 in} the formula, and has an alkyl group or phenyl group having 1 to 10 carbon atoms as R _{8 to} R ₁₁ . In addition, examples of the hydrocarbon group include a hydrocarbon group represented by C _n H _2n (n is 1 to 5), and the alkyl group having 1 to 10 carbon atoms includes a methyl group, an ethyl group, A propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, etc. are mentioned. Specific examples of such diaminopolysiloxane include 1,3-bis (3-aminopropyl) tetramethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (3- Aminopropyl) polydiphenylsiloxane and α, ω-bis (3-aminopropyl) polymethylphenylsiloxane. By comprising this, it contributes to the solubility and thermoplasticity of the obtained polyamic acid and polyimide resin in an organic solvent. Moreover, by using this, the glass transition temperature can be lowered, and it is particularly suitable for applications requiring low temperature processing.
The amount ratio of diaminopolysiloxane in the total diamine component in the polyimidesiloxane resin can be used in the range of 10 to 80 mol% of the total diamine component from the viewpoint of solubility and thermoplasticity, but from the viewpoint of heat resistance. Therefore, it is more preferable that the amount be in the range of 10 to 50 mol%. In particular, when 1,3-bis (3-aminopropyl) tetramethylsiloxane is used, solubility and thermoplasticity are improved without reducing heat resistance, which is preferable.

The equivalent ratio of the aromatic tetracarboxylic acid component to the total diamine component in the polymerization reaction of the polyimidesiloxane resin is an important factor that determines the molecular weight of the resulting polyimidesiloxane. It is well known that there is a correlation between the molecular weight and physical properties of a polymer, particularly the number average molecular weight and mechanical properties, and the larger the number average molecular weight, the better the mechanical properties. Therefore, in order to obtain a practically excellent strength, it is necessary to have a certain high molecular weight.
In the present invention, the equivalent ratio r of the acid component and the amine component is preferably a molar ratio of 0.95 ≦ r ≦ 1.05. Moreover, the range of 0.97 <= r <= 1.03 is more preferable from both mechanical strength and heat resistance. Moreover, there is no problem even if an end cap agent is used to control the molecular weight. Examples of the end cap agent include phthalic anhydride and trimellitic anhydride.
The mixing ratio of the solvent-soluble polyimide resin is not particularly limited, but 20 to 150 parts by weight of cyanate resin (A) (in the case of using cyanurate resin (E), cyanate resin + cyanurate resin) is 100 parts by weight. Particularly preferred is 30 to 120 parts by weight. When the solvent-soluble polyimide resin is less than the lower limit value, the flexibility of the film may be lowered, and when the upper limit value is exceeded, the thermal expansion coefficient may be increased.

  The reaction between the aromatic tetracarboxylic acid component and the diamine component is carried out by a known method in an aprotic polar solvent, and the final imide ring closure is better as the degree is higher. It is not preferable because imidization occurs due to heat and water is generated. Therefore, it is desirable to achieve an imidization ratio of 95% or more, more preferably 98% or more.

The solvent-soluble epoxy resin (C) used in the present invention is not particularly limited as long as it is a solvent-soluble epoxy resin. A solvent soluble in the epoxy resin will be described later. Examples of the epoxy resin include bis A type epoxy resin, bis F type epoxy resin, aromatic amine type epoxy resin, aminophenol type epoxy resin, and the like. An aralkyl-modified epoxy resin is particularly preferable. Thereby, the water absorption at the time of setting it as a resin layer can be reduced. Here, the aralkyl-modified epoxy resin refers to an epoxy resin having at least one aralkyl group in a repeating unit.
Further, conventionally, the cyanate resin alone has a problem that the curing rate is too fast and the curing reaction of the resin cannot be controlled, but in the present invention, the resin composition is obtained by combining the aralkyl-modified epoxy resin and the cyanate resin. The curing speed of the product can be adjusted. If the curing rate of the resin composition can be adjusted, the amount of resin flow can be adjusted during molding, and the thickness of the circuit board can be easily adjusted.

  Moreover, when an epoxy resin is present together with a cyanate resin, the cyanate resin forms a triazine ring by heating and then reacts with the epoxy resin to form a cyanurate ring. Here, since the triazine ring easily hydrolyzes by absorbing water, there is a problem in moisture resistance reliability, but the cyanurate ring does not cause hydrolysis.

  The blending ratio of the solvent-soluble epoxy resin is not particularly limited, but is preferably 20 to 200 parts by weight with respect to 100 parts by weight of cyanate resin (A) (cyanate resin + cyanurate resin when cyanurate resin (E) is used). In particular, 50 to 150 parts by weight are preferable. If the solvent-soluble epoxy resin is less than the lower limit, the effect of improving water absorption may be reduced, and if the upper limit is exceeded, the effect of improving the solder heat resistance at 260 ° C. may be reduced.

  Examples of the acid anhydride (D) used in the present invention include maleic anhydride, phthalic anhydride, acetic anhydride, trimellitic anhydride, nadic anhydride, allyl nadic anhydride, isobutyric anhydride, itaconic anhydride, Endomethylenetetrahydrophthalic anhydride, 4,4′-oxydiphthalic anhydride 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, Trifluoroacetic anhydride, trifluoromethanesulfonic anhydride, 1,2,4-benzenetricarboxylic anhydride, maleated methylcyclohexene tetrabasic anhydride, methylendomethylenetetrahydrophthalic anhydride and 2-methylpropionic anhydride Such as things. Among these, maleic anhydride is preferable.

  In the present invention, the acid anhydride acts as a catalyst for reacting the cyanate resin with the epoxy resin to promote the formation of a cyanurate ring. Thereby, even when the film is cured at a low temperature, no unreacted cyanate resin remains in the resin, and the cyanurate ring is formed from the triazine ring, so that the moisture resistance reliability can be improved. Furthermore, since the resin is cured at a low temperature, there is less stress accumulated in the resin than in the case of being cured at a high temperature, and therefore, the possibility of peeling between the base material such as copper is reduced.

  Moreover, as a compounding quantity of an acid anhydride (D), 0.01-20 weight part is used with respect to 100 weight part of cyanate resin (A) (When cyanurate resin (E) is used, cyanate resin + cyanurate resin). Preferably, it is 0.05 to 10 parts by weight.

Cyanurate resin (E) can be used for the resin composition of this invention. Examples of such cyanurate resin (E) include monoallyl diglycidyl isocyanuric acid (1-allyl-3,5-bis (2,3-epoxypropan-1-yl) -1,3,5-triazine-2,4, 6 (1H, 3H, 5H) -trione), diallyl monoglycidyl isocyanuric acid (1,3-diallyl-5- (2,3-epoxypropan-1-yl) -1,3,5-triazine-2,4 6 (1H, 3H, 5H) -trione) and the like. Among these, diallyl monoglycidyl isocyanuric acid and monoallyl diglycidyl isocyanuric acid are preferable.
In the present invention, by adding a cyanurate resin to the cyanate resin, the unreacted cyanate resin can be relatively reduced even when cured at a low temperature, and the cyanurate ring is used instead of the triazine ring causing hydrolysis. Therefore, the moisture resistance reliability can be improved.
Moreover, as a compounding quantity of cyanurate resin (E), it is preferable that the sum total of cyanate resin and cyanurate resin is 100 weight part, and cyanate resin is 40-0 weight part with respect to 60-100 weight part.

  The resin composition of the present invention can contain an inorganic filler (F). Thereby, reduction of a thermal expansion coefficient, heat resistance, and a flame retardance can be improved. Examples of such inorganic fillers include crystalline silica, pulverized silica, fused silica, spherical synthetic silica, alumina, magnesia, clay, talc, ceramic powder, glass fiber, calcium carbonate, barium sulfate, and mica, A plurality of types can be mixed and used. In particular, silica filler is preferable because it has a low dielectric constant and dielectric loss tangent and also has a low coefficient of thermal expansion. The average particle size of the inorganic filler is preferably 1.0 μm or less. More preferably, it is 0.5 μm or less. If it is larger than 1.0 μm, it cannot cope with the increase in wiring density of the multilayer wiring board, and there is a possibility that sufficient insulation reliability cannot be secured. The maximum particle size of the inorganic filler is preferably 5.0 μm or less, more preferably 2.0 μm or less. The maximum particle size of the inorganic filler can be controlled by filtering the inorganic filler solution.

In the present invention, the inorganic filler (F) is more preferably used by being dispersed in advance in the solvent (G). As a method of dispersing the inorganic filler in the solvent, the inorganic filler is added to the solvent, ultrasonic, three-roll, three-one motor, homogenizer, ball mill, rotation / revolution mixer, vacuum / revolution / revolution mixer, ultrasonic Examples of the dispersion method include a dispersion method, a high-pressure collision dispersion method, a high-speed rotation dispersion method, a bead mill method, a high-speed shear dispersion method, and a rotation and revolution dispersion method.
Moreover, as a ratio in the solvent of an inorganic filler, 5-75 weight% of the total weight of an inorganic filler solution is preferable. If it is less than 5% by weight, the viscosity of the inorganic filler solution may be low and the filler may easily settle, and if it exceeds 75% by weight, the viscosity of the inorganic filler solution may be high and handling may be difficult.

  By previously dispersing the inorganic filler in the solvent, the inorganic filler can be completely dispersed in the resin, and the thermal expansion coefficient of the resin composition can be reduced. Furthermore, it is easy to mix the resin in the solvent and the inorganic filler (F) solution when the surface of the inorganic filler is sufficiently wetted by the solvent.

  As a solvent (G) used for this invention, what is necessary is just to make the said polyimide resin (B) at least soluble, The said cyanate resin (A), the said polyimide resin (B), and the said epoxy resin (C) are It is better if it is a soluble solvent, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N, -methyl-2-pyrrolidone, 1,4-dioxane, gamma-butyllactone, diglyme, anisole , Cyclohexanone, toluene, xylene and the like. In particular, N-methyl-2-pyrrolidone having excellent solubility in a polyimide resin that requires the most amount of solvent is preferable. Moreover, since it is a polar solvent, an inorganic filler can be wetted, so it is suitable for dispersion. Only one type of solvent may be used, or two or more types may be mixed and used.

  In the resin composition of the present invention, an imidazole catalyst (H) can be used, whereby the curing of the cyanate resin can be accelerated and the reactivity of the resin composition can be freely controlled. Examples of such imidazole catalysts include 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5. -Hydroxymethylimidazole etc. are mentioned.

In this invention, as compounding quantity of each component, inorganic filler (Cyanate resin + cyanurate resin (Cyanate resin when using cyanurate resin (E) is used) is optionally added to 100 parts by weight of inorganic filler ( F) is preferably 5 to 400 parts by weight, more preferably 10 to 350 parts by weight, and still more preferably 50 to 300 parts by weight of the inorganic filler (F).
Moreover, as a compounding quantity of an imidazole-type catalyst (H), 0.0001-1 weight part is used with respect to 100 weight part of cyanate resin (A) (Cyanate resin + cyanurate resin when using cyanurate resin (E)). Preferably, it is 0.005-0.5 weight part.

  In addition to the above components, the resin composition of the present invention contains other additives such as a compatibilizing agent, a leveling agent, an antifoaming agent, a surfactant, an organic filler, and an antioxidant depending on the purpose. be able to. These additives can be used alone or in admixture of two or more. The content of the additive is not particularly limited, but is preferably 0.01 to 200 parts by weight with respect to 100 parts by weight of cyanurate resin (cyanate resin + cyanurate resin when cyanurate resin (E) is used). 0.1-100 weight part is preferable and 0.5-50 weight part is the most preferable.

  The resin composition of the present invention can be obtained by mixing a solution in which the inorganic filler (F) is dispersed in advance in the solvent (G) by the above method and other components. The mixing methods include three-one motor, ball mill, rotation / revolution mixer, vacuum / rotation / revolution mixer, ultrasonic dispersion method, high-pressure collision dispersion method, high-speed rotation dispersion method, bead mill method, high-speed shear dispersion method, and rotation. Examples include a method using various mixers such as a revolving dispersion method.

Next, the resin layer and the carrier material with the resin layer will be described.
FIG. 1 is a cross-sectional view showing a carrier material 1 with a resin layer in which a resin layer 3 composed of the above-described resin composition is formed on one side of a carrier material 2.

  The resin layer 3 is comprised with the resin composition mentioned above. Thereby, it is possible to obtain a resin layer which is excellent in electrical characteristics such as low dielectric constant and excellent in laser processability.

  Although the thickness of the resin layer 3 is not specifically limited, 0.1-60 micrometers is preferable and especially 1-40 micrometers is preferable. If the thickness of the resin layer is less than the lower limit value, the effect of improving the insulation reliability may be reduced. If the resin layer thickness exceeds the upper limit value, it is difficult to reduce the thickness of the circuit board. There is a case.

  As a manufacturing method of the resin layer of this invention, the method of apply | coating this to a carrier material by using the resin composition obtained above as a resin varnish is mentioned. Examples of the coating method include a film coater using a roll coater, a bar coater, a knife coater, a gravure coater, a die coater and a curtain coater, a spraying method, a dipping method, a printing machine, and a vacuum. Examples include a method using a printing machine and a dill pencer. Among these, a method using a die coater is preferable. Thereby, a resin layer having a predetermined thickness can be stably produced.

Examples of the carrier material 2 include metal foil made of copper or copper alloy, aluminum or aluminum alloy, polyethylene, fluorine resin, (aromatic) polyimide resin, polybutylene terephthalate, and polyester such as polyethylene terephthalate. Examples thereof include a resin film composed of a resin or the like. Among these, a resin film composed of a polyester resin is most preferable. This makes it particularly easy to peel from the resin layer with an appropriate strength. Furthermore, it has excellent stability against reactive diluents. Further, the resin composition component dissolved in the reactive diluent and the solvent can be prevented from migrating to the carrier material.
Although the thickness of the carrier material 2 is not specifically limited, 10-200 micrometers is preferable and 20-100 micrometers is especially preferable. When the thickness is within the above range, the flatness of the resin layer 3 is particularly excellent on the circuit.
As a method for producing the carrier material 1 with a resin layer, for example, a solution obtained by dissolving the above-described resin composition in a solvent is applied to the carrier material 2 with a thickness of about 1 to 100 μm, and the applied layer is, for example, 80 to It is dried at 140 ° C. for 20 seconds to 30 minutes, and preferably the residual solvent amount is 0.5% by weight or less. Thereby, the carrier material 1 with a resin layer in which the resin layer 3 is laminated on the carrier material 2 can be obtained. The heat curing temperature of the resin composition is not particularly limited, but is preferably 140 to 300 ° C, and particularly preferably 140 to 250 ° C.

Next, the circuit board will be described.
FIG. 2 is a cross-sectional view showing an example of the circuit board of the present invention.
As shown in FIG. 2, the circuit board 10 includes a core substrate 5 and a resin layer 3 provided on both surfaces of the core substrate 5.
The core substrate 5 is formed with an opening 51 opened by a drilling machine. Conductor circuits 52 are formed on both surfaces of the core substrate 5.
The inside of the opening 51 is plated, and the conductor circuits 52 on both surfaces of the core substrate 5 are conducted.
The resin layer 3 is provided on both surfaces of the core substrate 5 so as to cover the conductor circuit 52. An opening 31 formed by laser processing is formed in the resin layer 3.
Conductor circuits 32 are formed on both surfaces of the resin layer 3.
The conductor circuit 52 and the conductor circuit 32 are electrically connected via the opening 31.

As a method of manufacturing such a circuit board, for example, an opening 51 is formed in a core substrate (for example, FR-4 double-sided copper foil) 5 by drilling with a drill machine, and then by electroless plating. A plating process is applied to 51 so as to make both surfaces of the core substrate 5 conductive. Then, the conductor circuit 52 is formed by etching the copper foil of the core substrate.
The conductor circuit 52 may be made of any material as long as it is suitable for this manufacturing method, but is preferably removable by a method such as etching or peeling in the formation of the conductor circuit. Those having resistance to the chemicals used in this are preferred. Examples of the material of the conductor circuit 52 include copper, copper alloy, 42 alloy, nickel, and the like. In particular, the copper foil, the copper plate, and the copper alloy plate are most preferable for use as the conductor circuit 52 because not only electrolytic plated products and rolled products can be selected, but also various thicknesses can be easily obtained.

Next, the resin layer 3 is formed so as to cover the conductor circuit 52.
Examples of a method for forming the resin layer 3 include a method of pressing the above-described carrier material with a resin layer. Specifically, the carrier material with a resin layer is vacuum-pressed, an atmospheric laminator, a vacuum laminator, and a becquerel type. The method of laminating using a laminating apparatus etc. and forming the resin layer 3 is mentioned.
When a metal layer is used as the carrier material, the metal layer can be processed as a conductor circuit.

Next, after peeling off the carrier material, the formed resin layer 3 is heated and cured.
The temperature for heating and curing is preferably in the range of 140 ° C to 300 ° C. In particular, 140-250 degreeC is preferable. Further, one or more resin layers 3 are further formed on the resin layer 3 formed by heating and semi-curing the first resin layer 3, and the semi-cured resin layer 3 is heat-cured again to such an extent that there is no practical problem. By doing so, the adhesion between the resin layers 3 and between the resin layer 3 and the conductor circuit 52 can be improved. In this case, the semi-curing temperature is preferably 80 ° C to 200 ° C, more preferably 80 ° C to 140 ° C.

  Moreover, after forming the resin layer 3, the adhesion between the resin layers 3 and between the resin layer 3 and the conductor circuit 52 can be improved by performing plasma treatment on the surface of the resin layer 3. As a gas for plasma treatment, oxygen, argon, fluorine, carbon fluoride, nitrogen, or the like can be used singly or in combination. Further, the plasma treatment may be performed a plurality of times.

Next, the resin layer 3 is irradiated with a laser to form the opening 31.
As the laser, an excimer laser, a UV laser, a carbon dioxide gas laser, or the like can be used. Formation of the opening 31 by the laser can easily form the fine opening 31 regardless of whether the material of the resin layer 3 is photosensitive or non-photosensitive. Therefore, it is particularly preferable when the resin layer 3 needs to be finely processed.

Next, the conductor circuit 32 is formed.
The conductive circuit 32 can be formed by a known method such as a semi-additive method. A circuit board can be obtained by these methods.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

Example 1
1. Synthesis of polyimide siloxane (PI) 791 g of dehydrated and purified N-methyl-2-pyrrolidone (NMP) was placed in a four-necked flask equipped with a dry nitrogen gas inlet tube, a cooler, a thermometer, and a stirrer, and nitrogen gas was allowed to flow. Stir vigorously for 10 minutes. Next, 2,2-bis (4- (4-aminophenoxy) phenyl) propane (BAPP) 73.8926 g (0.180 mol), 1,3-bis (3-aminophenoxy) benzene 17.5402 g (0 .060 mol), α, ω-bis (3-aminopropyl) polydimethylsiloxane 50.2200 g (average molecular weight 837, 0.060 mol) is added and the system is heated to 60 ° C. and stirred until uniform. . After homogeneous dissolution, the system was cooled to 5 ° C. with an ice-water bath, and 43.1330 g (0.150 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), 3,3 ′ , 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) 48.4110 g (0.150 mol) was added in powder form over 15 minutes, and then stirring was continued for 3 hours. During this time, the flask was kept at 5 ° C.

  Thereafter, the nitrogen gas inlet tube and the cooler were removed, a Dean-Stark tube filled with xylene was attached to the flask, and 198 g of xylene was added to the system. Instead of the oil bath, the system was heated to 175 ° C., and generated water was removed from the system. When heated for 4 hours, no water was observed from the system. After cooling, this reaction solution was put into a large amount of methanol to precipitate polyimidesiloxane. The solid content was filtered and then dried under reduced pressure at 80 ° C. for 12 hours to remove the solvent to obtain 227.79 g (yield 92.1%) of a solid resin. When the infrared absorption spectrum was measured by the KBr tablet method, an absorption of 5.6 μm derived from a cyclic imide bond was observed, but an absorption of 6.06 μm derived from an amide bond could not be recognized. It was confirmed that it was almost 100% imidized.

2. Preparation of Resin Varnish First, 67 g of spherical silica (average particle size 0.5 μm) was added in advance to 36 g of NMP as an inorganic filler, and dispersed with a vacuum defoaming kneader / stirrer to prepare a silica slurry. Next, 20 g of the above polyimidesiloxane (PI), phenol novolac polycyanate resin (Lonza Co., Ltd., trade name: PrimasetPT-30), aralkyl-modified epoxy resin (Nippon Kayaku Co., Ltd., trade name: NC-3000) 40 g, 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: 2PHZ-PW) 0.7 g and maleic anhydride (manufactured by Wako Pure Chemical Industries) 0. 7 g and NMP 100 g were mixed, and stirred and dissolved in a rotation / revolution mixer to prepare a resin composition varnish.

3. Production of Carrier Material with Resin Layer The resin varnish obtained above was formed with a die coater on a polyester film as a carrier material to a thickness of 20 μm to obtain a carrier material with a resin layer.

4). 4.1 Production of Circuit Board 4.1 Formation of Inner Layer Circuit and Resin Layer Using a double-sided copper-clad laminate (ELC-4781 manufactured by Sumitomo Bakelite Co., Ltd.) having a total thickness of 0.3 mm and a copper foil thickness of 12 μm, After opening with a drill machine, conduction between the upper and lower copper foils was achieved by electroless plating, and the inner layer conductor circuits were formed on both sides by etching the copper foils on both sides.
Next, the surface of the inner layer conductor circuit is sprayed with a chemical solution mainly composed of hydrogen peroxide and sulfuric acid (Tech SO-G manufactured by Asahi Denka Kogyo Co., Ltd.), thereby forming irregularities by roughening treatment. The resin layer of the carrier material with a resin layer obtained above was bonded to the inner conductor circuit surface, and the conductor circuit was embedded in the resin layer using a vacuum laminator, and a nitrogen atmosphere at 200 ° C. for 60 minutes. A lower baking treatment was performed to form a resin layer.

4.2 Laser processing and formation of outer layer circuit Next, using a UV-YAG laser device (ML605LDX manufactured by Mitsubishi Electric Corporation), an opening (blind via hole) with a diameter of 40 μm is formed, and desmear treatment (Nippon McDormid) (Manufactured by Macudizer series). Electroless copper plating (Sulcup PRX manufactured by Uemura Kogyo Co., Ltd.) was performed for 15 minutes to form a power feeding layer having a thickness of 0.5 μm. In the desmear treatment, a monoethanolamine solution (R-100, manufactured by Mitsubishi Gas Chemical Co., Ltd.) is used for the first-stage alkaline aqueous solution layer, and permanganic acid is used for the second-stage oxidizing resin etchant. Aqueous solutions containing potassium and sodium hydroxide as main components (Nippon McDermid Co., Ltd. Macudizers 9275 and 9276) and acidic amine aqueous solutions (Nippon McDermid Co., Ltd. Macudizer 9279) were used for neutralization.
Next, an ultraviolet photosensitive dry film (AQ-2558 manufactured by Asahi Kasei Co., Ltd.) having a thickness of 25 μm for plating resist is bonded to the surface of the power feeding layer with a hot roll laminator, and the minimum line width / line spacing is 20/20 μm. After aligning using a chromium vapor deposition mask (made by Towa Process Co., Ltd.) on which a pattern of 1 was drawn, exposure was performed using an exposure apparatus (UX-1100SM-AJN01 made by USHIO INC.). Next, it developed with the sodium carbonate aqueous solution, and the plating resist in which the pattern was formed was formed.

Next, electrolytic copper plating (Okuno Pharmaceutical Co., Ltd. 81-HL) is performed at 3 A / dm ² for 30 minutes in the opening where the pattern obtained above is formed using the power feeding layer as an electrode, and the thickness is about 20 μm. The copper wiring was formed. Here, the plating resist was peeled off using a two-stage peeling machine.

  Next, the power feeding layer was etched and removed by immersing it in an aqueous ammonium persulfate solution (AD-485 manufactured by Meltex Co., Ltd.) to ensure insulation between the wirings. Finally, a dry film type solder resist (CFP-1211 manufactured by Sumitomo Bakelite Co., Ltd.) was formed on the circuit surface while embedding the circuit with a vacuum laminator, and finally a circuit board was obtained.

(Example 2)
The procedure was the same as Example 1 except that the acid anhydride was changed to phthalic anhydride.

(Example 3)
Example 1 was repeated except that the acid anhydride was trimellitic anhydride.

Example 4
The same procedure as in Example 1 was conducted except that the cyanate resin was changed to bisphenol A cyanate ester (Ciba, trade name: AroCy B-10).

(Example 5)
The same procedure as in Example 1 was performed except that the cyanate resin was changed to bisphenol A cyanate ester (Ciba, trade name: AroCy F-10).

(Comparative Example 1)
The procedure was the same as Example 1 except that the acid anhydride was not mixed.

(Comparative Example 2)
The same procedure as in Example 1 was conducted except that the acid anhydride was not mixed and the curing temperature was 250 ° C./3 hrs.

The following evaluation was performed about the resin layer and circuit board which were obtained above. The evaluation items are shown together with the contents. The obtained results are shown in Table 1.
1. Dielectric constant The dielectric constant was evaluated by the perturbation method.

2. Dielectric loss tangent Dielectric loss tangent was evaluated by the perturbation method.

3. Linear expansion coefficient The linear expansion coefficient was evaluated with a thermal strain measuring apparatus.

4). Adhesiveness Adhesiveness was evaluated by a cross cut test (JIS K5400-1900).
A: Each cut is thin and smooth on both sides, and there is no peeling between the intersection and the square at a glance.
○: There is a slight peeling at the intersection of the cuts, there is no peeling at a glance, and the area of the defect is within 5% of the total square area.
Δ: There are peeling at both sides of the cut and at the intersection, and the area of the defect is 5% or more ×: the area of the peeling is 65% or more

5. Crack resistance The crack resistance was evaluated by conducting a temperature cycle test of -55 ° C to 125 ° C 1,000 times, observing the surface and cross-section of the circuit board, and visually evaluating the presence or absence of cracks in the resin layer. Each code is as follows.
◎: More than 500 times in the temperature cycle test and no cracks in the resin layer up to 1,000 times ○: More than 200 times in the temperature cycle test and no cracks in the resin layer up to 500 times △: 50 in the temperature cycle test No more cracks in the resin layer up to 200 times x: Cracks occur in the resin layer up to 50 times in the temperature cycle test Insulation degradation resistance characteristics The insulation degradation degradation characteristics were evaluated by measuring a high-temperature and high-humidity bias test at 85 ° C./85%/5.0 V, and measuring insulation resistance values. Each code is as follows.
A: 100 MΩ is maintained at 1000 hrs in the high temperature and high humidity bias test. ○: 100 MΩ is maintained at 500 hrs in the high temperature and high humidity bias test. Δ: 100 MΩ is maintained at 100 hrs in the high temperature and high humidity bias test. 100MΩ cannot be maintained within 100hrs in high temperature and high humidity bias test

  As is clear from Table 1, Examples 1 to 3 had a low dielectric constant and dielectric loss tangent, and were excellent in laser processability, linear expansion coefficient, adhesion, crack resistance, and moisture resistance reliability. 1 had a problem with moisture resistance reliability, and Comparative Example 2 had a problem with crack resistance.

The resin layer obtained using the resin composition of the present invention is suitable for applications such as circuit boards, printed wiring boards, multilayer wiring boards, semiconductor devices, and liquid crystal display devices. Since the resin composition of the present invention has excellent dielectric properties in the GHz band and excellent heat resistance, it has mounting reliability and interlayer connection reliability, and also has excellent laser processability. It is.
When using the resin composition of the present invention as an interlayer insulating film of a circuit board, a method such as coating on a circuit board or pressing a carrier film with a resin layer coated on a carrier film is conceivable. Therefore, it is preferable to form a resin layer on the carrier film and embed the carrier film with the resin layer by pressing.

It is sectional drawing which shows an example of the carrier material with a resin layer of this invention. It is sectional drawing which shows an example of the circuit board of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Carrier material with resin layer 2 Carrier material 3 Resin layer 31 Opening part 32 Conductor circuit 5 Core substrate 51 Opening part 52 Conductor circuit 10 Circuit board

Claims (16)

A resin composition comprising a cyanate resin (A), a solvent-soluble polyimide resin (B), a solvent-soluble epoxy resin (C), and an acid anhydride (D). The cyanate resin (A) includes at least a cyanate compound represented by the general formula (1), a cyanate compound represented by the general formula (2), and a cyanate group of these compounds trimmed at 40% or less, The resin composition according to claim 1, which is at least one cyanate compound selected from among cyanate compounds having two or more cyanate groups.
(In Formula (1), R < ₁ > -R < ₆ > shows either a hydrogen atom, a methyl group, a fluoroalkyl group, and a halogen atom each independently.)
(In the formula _(2), R 1 to R ₃ are each independently a hydrogen atom, one of methyl group, a fluoroalkyl group and a halogen atom, n is an integer from 0 to 6.) The resin composition according to claim 1, wherein the solvent-soluble polyimide resin (B) is a polyimide siloxane resin. The polyimidesiloxane resin includes 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic acid At least one aromatic tetracarboxylic acid component selected from an anhydride and 4,4′-diphenylsulfonetetracarboxylic dianhydride, and 10 to 80 mol% of a diaminopolysiloxane represented by the general formula (3) The resin composition according to claim 3, wherein the resin composition is synthesized by reacting a diamine component comprising 20 to 90 mol% of an aromatic diamine.
(In the formula (3), _{R 7} represents a hydrocarbon _group, R 8 _{to R 11} represents an alkyl group or a phenyl group having 1 to 10 carbon atoms, n is an integer from 1 to 20.) The resin composition according to any one of claims 1 to 4, wherein the solvent-soluble epoxy resin (C) is an aralkyl-modified epoxy resin. The resin composition according to claim 1, wherein the acid anhydride (D) is maleic anhydride. The resin composition according to claim 1, wherein the resin composition contains a cyanurate resin (E). The resin composition according to claim 1, wherein the resin composition contains an inorganic filler (F). The resin composition according to claim 8, wherein the inorganic filler (F) is silica. The resin composition according to claim 8 or 9, wherein the inorganic filler (F) has an average particle diameter of 1 µm or less. The resin composition according to any one of claims 8 to 10, wherein the inorganic filler is obtained by previously dispersing the polyimide resin in a soluble solvent (G). The resin composition according to claim 11, wherein the solvent (G) soluble in the polyimide resin is N-methyl-2-pyrrolidone. Furthermore, the resin composition in any one of Claims 1-12 which comprises an imidazole series catalyst (H). A resin layer comprising the resin composition according to claim 1. A resin material with a resin layer, wherein the resin layer according to claim 14 is formed on at least one surface of the carrier material. A circuit board comprising the resin layer according to claim 14.