JP2009040919A - Thermosetting resin composition, resin film using the same, laminate and prepreg - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which excels in a dielectric constant and storage stability and has adhesion to an electrically conductive layer. <P>SOLUTION: The thermosetting resin composition comprises an epoxy resin, a curing agent, a curing accelerator, and an organic solvent, wherein: the curing agent comprises an active ester type curing agent and the content of the active ester type curing agent is 50-200 pts.wt. based on 100 pts.wt. epoxy resin; the curing accelerator comprises an imidazole compound and a phosphorus compound; and the content of the curing accelerator is 0.8-10 pts.wt. based on 100 pts.wt. the active ester type curing agent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermosetting resin composition, and in particular, to a thermosetting resin composition excellent in dielectric constant and dielectric loss tangent, and a resin film, a laminate, and a prepreg using the same.

  Conventionally, various techniques for improving the effect of dielectric constant and storage stability have been proposed in thermosetting resin compositions.

  For example, in Patent Document 1, an epoxy resin, an active ester compound, imidazole and 3 as a curing accelerator are provided for the purpose of providing an epoxy resin composition or the like that provides a low dielectric loss tangent and a fast curing rate and is excellent in storage stability. Resin compositions that are secondary amines are disclosed. And this literature 1 describes that imidazole and a tertiary amine are 0.2-1.5 weight part with respect to an epoxy resin (Claims).

However, further improvements in dielectric constant and dielectric loss tangent are desired over such conventional thermosetting resin compositions.
JP 2003-261650 A

  Then, the objective of this invention is providing the thermosetting resin composition excellent in the dielectric constant and the dielectric loss tangent.

  Moreover, the other objective of this invention is to provide said thermosetting resin composition, and a resin film, a laminated board, and a prepreg using this.

  As a result of diligent research, the present inventor has found that a phenomenon such as a problem in the prior art is caused by blocking air or curing in a low oxygen state. Furthermore, the knowledge that the resin composition which consists of a specific composition can achieve the objective of this invention was acquired. The present invention provides an invention having the following configuration.

1. In a resin composition comprising an epoxy resin, a curing agent, a curing accelerator, and an organic solvent,
The curing agent contains an active ester type curing agent, and the active ester type curing agent is 50 to 200 parts by weight with respect to 100 parts by weight of the epoxy resin,
The curing accelerator includes an imidazole compound and a phosphorus compound, and the content of the curing accelerator is 0.8 to 10 parts by weight with respect to 100 parts by weight of the active ester type curing agent. A thermosetting resin composition.

2. 2. The thermosetting resin composition as described in 1 above, wherein a weight ratio of the imidazole compound and the phosphorus compound is 1: 0.5 to 1: 1.3.

3. 3. The thermosetting resin composition as described in 1 or 2 above, wherein the imidazole compound has a triazine ring.

4). 2. The thermosetting resin composition as described in 1 above, wherein the total amount of the curing accelerator is 2.5 to 6 parts by weight with respect to 100 parts by weight of the total amount of the active ester type curing agent.

5). The thermosetting resin composition as described in 1 above, further comprising an inorganic filler.

6). 6. The thermosetting resin composition as described in 5 above, wherein the inorganic filler is a layered silicate and / or silica.

7. The resin film formed by performing the process which volatilizes the organic solvent in the thermosetting resin composition in any one of said 1-6, and forming in a film form.

8). A laminate comprising a conductive layer.

9. A prepreg obtained by impregnating a base material with the thermosetting resin composition according to any one of 1 to 6 above and volatilizing an organic solvent.

10. A laminate comprising a conductive layer formed on any of the resin composition according to any one of 1 to 6, the resin film according to 7 or the prepreg according to 9.

  ADVANTAGE OF THE INVENTION According to this invention, the thermosetting resin composition excellent in the dielectric constant and dielectric loss tangent, and the resin film, laminated board, and prepreg which use this are provided.

Hereinafter, the thermosetting resin composition of the present invention will be described in detail based on preferred embodiments. As described above, the composition of the present invention is a resin composition comprising an epoxy resin, a curing agent, a curing accelerator, and an organic solvent.
The curing agent contains an active ester type curing agent, and the active ester type curing agent is 50 to 200 parts by weight with respect to 100 parts by weight of the epoxy resin,
The curing accelerator includes an imidazole compound and a phosphorus compound, and the content of the curing accelerator is 0.8 to 10 parts by weight with respect to 100 parts by weight of the active ester type curing agent. To do.

In this way, the composition of the present invention, in particular with respect to the active ester type curing agent (also with respect to the epoxy resin), blends more curing accelerators than usual, so that the electrical properties such as dielectric constant and dielectric loss tangent are increased. Improved characteristics.
In addition, the normal here refers to the quantity of the hardening accelerator described in the Example in the above-mentioned patent document 1, for example.

  The curing accelerator used in the present invention contains an imidazole compound and a phosphorus compound, but the mixing ratio of the weight ratio of the imidazole compound and the phosphorus compound is sufficient for both curability and storage stability. In this point, it is preferably 1: 0.5 to 1: 1.3, and more preferably 1: 0.6 to 1: 1.1.

Although it does not restrict | limit especially as an imidazole type compound, For example, what has a triazine ring, what has a cyano group, what has an alkoxy group, etc. are mentioned, These compounds are 1 type (s) or 2 or more types. Used.
Among them, a compound having a triazine ring (triazine ring-containing imidazole compound) is preferable in that the dielectric constant and dielectric loss tangent are further improved and the adhesion to metal is good.

  Specific examples of the triazine ring-containing imidazole compound include 2,4-diamino-6- (2′-methylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- (2′-undecylimidazolyl) ethyl. -S-triazine, 2,4-diamino-6- (2'-methyl-4-methylimidazolyl) ethyl-s-triazine, and their isocyanuric acid adducts.

  In addition, the phosphorus compound is not particularly limited, and examples thereof include triphenylphosphine, tri-o-tolylphosphine, tri-n-butylphosphine, triphenylphosphite, and the like. Or it is used by 2 or more types.

  In the composition of the present invention, the content of the curing accelerator is 0.8 to 10 parts by weight with respect to 100 parts by weight of the active ester curing agent. . When the amount exceeds 10 parts by weight, the curing accelerator is difficult to uniformly disperse in the cured body, and the curing accelerator tends to bleed out or the uniformity of curing cannot be obtained, resulting in adhesion to the conductive layer. descend. In particular, the amount is preferably 2.5 to 6 parts by weight from the viewpoint that curing proceeds sufficiently and the curing accelerator can be uniformly dispersed in the cured body.

  The curing agent used in the composition of the present invention contains an active ester type curing agent. Examples of the active ester type curing agent include active esters described in JP-A Nos. 2002-12650 and 2004-169021.

The content of the active ester type curing agent is 50 to 200 parts by weight with respect to 100 parts by weight of the epoxy resin. In particular, it is desirable to contain 90 to 200 parts by weight of an active ester type curing agent with respect to 100 parts by weight of the epoxy resin in that the dielectric constant and dielectric loss tangent at high frequencies can be reduced.
When viewed in terms of equivalent ratio, if the ratio of the epoxy equivalent of the epoxy resin to the equivalent of the active ester type curing agent is 1: 1.6 to 1: 4, the dielectric constant and dielectric loss tangent at high frequencies can be reduced. it can. Furthermore, the ratio of the epoxy equivalent to the equivalent of the active ester type curing agent is preferably 1: 2 to 1: 3.

  In addition to the active ester type curing agent, for example, a known curing agent such as a phenol compound, an acid anhydride compound, or dicyandiamide can be used as the curing agent.

  Examples of the epoxy resin as the thermosetting resin used in the composition of the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol M type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, aromatic Examples thereof include amine-type epoxy resins, aminophenol-type epoxy resins, dicyclopentadiene-type epoxy resins, and alkylphenol-type epoxy resins. In particular, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin are preferable.

  The resin composition of the present invention can contain a polyvinyl acetal resin, a phenoxy resin, a polyphenylene ether resin, or the like as a resin other than an epoxy resin. A polyvinyl acetal resin is preferable in that it is excellent in adhesion strength with copper bonding when used for a copper-clad laminate. As a polyvinyl acetal resin, that whose molecular weight is 5000-1 million is preferable.

  Although it does not specifically limit as a manufacturing method of the said polyvinyl acetal resin, For example, polyvinyl alcohol (PVA) is melt | dissolved in warm water or hot water, The obtained PVA aqueous solution is predetermined temperature (for example, 0-95 degreeC). ) And an aldehyde and an acid catalyst are added, and the acetalization reaction proceeds while stirring, and then the reaction is completed by raising the reaction temperature and aging, followed by neutralization, water washing and drying. The method of obtaining a powdery polyvinyl acetal resin through various processes is mentioned.

  Although it does not specifically limit as aldehyde used for manufacture of the said polyvinyl acetal resin, For example, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, n-hexyl aldehyde, 2-ethyl Examples include butyraldehyde, benzaldehyde, cinnamaldehyde, and the like. These aldehydes may be used alone or in combination of two or more.

  The organic solvent used in the composition of the present invention is not particularly limited. For example, DMF (N, N-dimethylformamide), MEK (methyl ethyl ketone), MIBK (methyl isobutyl ketone), NMP (N— Methyl-pyrrolidone), toluene and the like, and these compounds may be used alone or in combination.

The composition of the present invention preferably further contains an inorganic filler from the viewpoint of improving dimensional stability.
Examples of the inorganic filler include layered silicates; fused silica, colloidal silica, fumed silica, baked silica, precipitated silica, silica such as ground silica; and aluminum hydroxide.
In particular, a layered silicate and / or silica is preferable in that high dispersibility in the resin can be easily realized.

When layered silicate is used as the inorganic filler, the content thereof is preferably 0.05 to 7 parts by weight, particularly 0.1 to 4 parts by weight with respect to 100 parts by weight of the epoxy resin and the curing agent. .
When the amount is too large, the viscosity of the composition becomes high and handling properties are deteriorated. When the amount is too small, improvement in mechanical properties such as dimensional stability cannot be obtained.

When silica is used as the inorganic filler, the content thereof is preferably 10 to 75 parts by weight, particularly preferably 20 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin and the curing agent.
When the amount is too large, the dielectric constant increases. When the amount is too small, improvement in mechanical properties such as dimensional stability cannot be obtained.

  In the resin composition of the present invention, if necessary, a solvent other than an organic solvent, a flame retardant, a filler other than an inorganic filler (for example, an organic filler, an organic-inorganic composite filler, etc.), an antioxidant, Coloring agents and the like can be added.

  The method for producing the resin composition of the present invention and the subsequent curing method are not particularly limited.

Moreover, the following method can be mentioned as an example of the manufacturing method of a buildup board | substrate.
Laminate the resin sheet from which the protective sheet is peeled off from the sheet-shaped resin laminate on the FR-4 substrate on which the base circuit is formed (the base sheet peels off)-cure-surface treatment for plating-copper Plating-forming a circuit pattern (resist coating, exposure, etching), laminating a sheet-like resin laminate (applying a material that has not been made into a sheet-like laminate beforehand, and evaporating and drying the solvent), heat curing, ( Thereafter, the multilayer laminated substrate is formed 6 times repeatedly, and the final heat curing is performed. Heat curing in each step can perform aging of copper plating and crystal growth simultaneously with curing of the resin sheet. Moreover, the residual stress with the cured resin sheet, the copper plating, and the resin sheet to be cured can be reduced.

Applying a resin composition containing a solvent to a base substrate-Volatilizing the solvent-Curing-Surface treatment for plating-Plating-Forming a test pattern (resist coating, exposure, etching), solvent Is applied to a base substrate (hereinafter repeated), and finally cured.
The formation of the via hole and the through hole may be appropriately performed by a usual method.

  The resin composition of the present invention is not particularly limited in its use, but as a form of the resin film, prepreg, laminate, etc. described below or in the state of the composition, for example, an adhesive, a semiconductor sealing agent, a film Used for adhesives, interlayer insulating materials, etc.

Moreover, according to this invention, the process which volatilizes the organic solvent in the thermosetting resin composition mentioned above is performed, and the resin film formed in a film form is provided.
In this process, a curing process or a chemical process is performed.
The curing treatment refers to a treatment in which the thermosetting resin composition is heated for 30 minutes or more at a temperature at which the curing reaction sufficiently reacts (for example, 150 ° C.).
The chemical treatment refers to a treatment for eluting the solvent of the thermosetting resin composition by dipping in a swelling liquid and / or a roughening liquid for a total of 5 minutes or more.

  Moreover, according to this invention, the laminated board formed by forming the electrically conductive layer which consists of plating and copper foil lamination | stacking is provided.

  Moreover, according to this invention, the prepreg formed by impregnating a base material with the thermosetting resin composition mentioned above and volatilizing an organic solvent is provided.

  Moreover, according to this invention, the laminated board formed by forming the electrically conductive layer which consists of plating and copper foil in either the resin composition mentioned above, a resin film, or the prepreg mentioned above is provided.

  Here, the conductive layer means a layer capable of transmitting an electrical signal, and examples thereof include metals, conductive resins, and conductive carbon. The conductive layer may be formed with a circuit pattern or a terminal.

  For the plating, copper, gold, silver, or the like can be used. As a forming method, a known method can be adopted, and the resin composition is formed by electroless plating or electroless plating and further electrolytic plating. Prior to electroless plating, a fine uneven shape may be imparted to the surface by plasma treatment or chemical treatment.

  As the copper foil, a known copper foil can be used. In particular, when roughened copper having fine irregularities formed on the surface is used, the adhesiveness is excellent when laminated using the roughened surface of the copper foil on the resin side.

  A known method can be used as a laminating method for producing the laminated plate, and examples thereof include press molding and roll compression molding. In molding, the layers may be laminated in a vacuum state.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples.

First, the evaluation items, apparatus and measurement method, and judgment criteria for the cured product adjusted in Examples described later are shown below.
[Dielectric constant induction and electrotangent (1 GHz capacity method)]
An RF impedance / material analyzer E4991A manufactured by Agilent Technologies was used. As the sample, eight pieces of a film-like cured body having a thickness of about 50 μm cut into 2 cm squares were stacked and placed on a measuring jig, and the dielectric constant and dielectric loss tangent were measured.

[Adhesion with copper foil]
A copper-clad laminate was prepared, and five pieces obtained by cutting the copper-clad laminate into a size of 1 cm × 15 cm were prepared, immersed in a solder bath at 260 ° C. for 30 seconds, and taken out. Thereafter, the copper plating surface was observed and peeled off from the resin sheet and visually confirmed. In the case where there is peeling, a swelling or trace of swelling is observed on the copper foil side.

  The evaluation results of the cured products produced in the following examples and comparative examples are shown at the end of each example.

Silica (EXR-3, manufactured by Tatsumori) 98 g Triazine ring-containing imidazole compound (2,4-diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine isocyanuric acid as a curing accelerator Addition product, 2MA-OK, manufactured by Shikoku Kasei Kogyo Co., Ltd. (1.3 g) and triphenylphosphine (manufactured by Wako Pure Chemical Industries, Ltd.) 1.3 g were added to DMF 316 g, mixed well, and stirred at room temperature until a completely homogeneous solution was obtained. did. Next, 123 g of epoxy resin “HP-7200H (Dainippon Ink and Chemicals)” was added and stirred at room temperature until a completely homogeneous solution was obtained. Then, active ester curing agent (Dainippon Ink and Chemicals Ltd., EXB-9451) and 100g was charged to the above solution and stirred at room temperature until completely homogeneous solution, to prepare a resin composition solution.

The resin composition solution obtained above was dried using an applicator on a transparent polyethylene terephthalate (PET) film (trade name “PET5011 550”, thickness 50 μm, manufactured by Lintec Co., Ltd.) subjected to a release treatment. Was dried in a gear oven at 100 ° C. for 12 minutes to prepare a laminate of an uncured resin-like resin composition of 180 mm × 250 mm × 50 μm and a PET film.
Next, the laminate was heated in a gear oven at 170 ° C. for 1 hour to produce a laminate in which the film-like resin composition was semi-cured.

The PET film was peeled from the laminate, and the semi-cured film-shaped resin composition was heated in a gear oven at 180 ° C. for 3 hours to prepare a film-shaped cured body.
Two sheets of an uncured product of a film-shaped resin composition of 180 mm × 250 mm × 50 μm and a laminate of a PET film are bonded to each other, and the uncured product of the film-shaped resin composition is bonded to each other, and the PET film on one side is peeled off. The film was placed on a SUS plate having a smooth surface between the press dies of the vacuum press so that the film was on the lower side.
Next, a 180 cm × 20 cm × 25 μm roughened copper foil was placed on a resin sheet, a SUSU plate with a smooth surface was placed, and pressure-bonded at 180 ° C. and 10 MPa for 30 minutes.
After taking out from the vacuum press, heat treatment was performed in a gear oven at 180 ° C. for 3 hours to prepare a copper-clad laminate.
Dielectric constant of the film-like cured product is 3.09 and the dielectric loss tangent is 0.041.
Good adhesion with copper foil: 5 pieces.

A film-like cured product was prepared in the same manner as in Example 1 except that the imidazole compound (2-phenylimidazole isocyanuric acid adduct, 2PZ-OK, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was used as the curing accelerator.
Dielectric constant 3.16, dielectric loss tangent 0.051
Good adhesion with copper foil: 5 pieces.

(Comparative Example 1)
A cured film was prepared in the same manner as in Example 1 except that the total of the triazine ring-containing imidazole compound + phosphorus compound was 0.26 g + 0.26 g as a curing accelerator.
Dielectric constant 3.20, dielectric loss tangent 0.064
Adhesion with copper foil: Swelling was observed ... 3, and copper foil and resin sheet were peeled ... 2 pieces.

(Comparative Example 2)
A film-like cured product was produced in the same manner as in Example 1 except that the total of the triazine ring-containing imidazole compound + phosphorus compound was only 5.0 g + 5.0 g as a curing accelerator.
Dielectric constant 3.14, dielectric loss tangent 0.051
Adhesion with copper foil Swelling was observed ... 5 pieces.

  INDUSTRIAL APPLICABILITY The present invention has industrial applicability as a thermosetting resin composition excellent in dielectric constant and dielectric loss tangent, and as a resin film, laminate, and prepreg using the same.

Claims (10)

In a resin composition comprising an epoxy resin, a curing agent, a curing accelerator, and an organic solvent,
The curing agent contains an active ester type curing agent, and the active ester type curing agent is 50 to 200 parts by weight with respect to 100 parts by weight of the epoxy resin,
The curing accelerator includes an imidazole compound and a phosphorus compound, and the content of the curing accelerator is 0.8 to 10 parts by weight with respect to 100 parts by weight of the active ester type curing agent. A thermosetting resin composition.   The thermosetting resin composition according to claim 1, wherein a weight ratio of the imidazole compound and the phosphorus compound is 1: 0.5 to 1: 1.3.   The thermosetting resin composition according to claim 1, wherein the imidazole compound has a triazine ring.   2. The thermosetting resin composition according to claim 1, wherein the total amount of the curing accelerator is 2.5 to 6 parts by weight with respect to 100 parts by weight of the total amount of the active ester curing agent. object   The thermosetting resin composition according to claim 1, further comprising an inorganic filler.   The thermosetting resin composition according to claim 5, wherein the inorganic filler is a layered silicate and / or silica.   A resin film formed by performing a process of volatilizing an organic solvent in the thermosetting resin composition according to any one of claims 1 to 6 and forming a film.   A laminated board comprising a conductive layer made of a plating and copper foil laminate.   A prepreg obtained by impregnating a base material with the thermosetting resin composition according to claim 1 and volatilizing an organic solvent.   A conductive layer comprising plating and copper foil lamination is formed on any of the resin composition according to any one of claims 1 to 6, the resin film according to claim 7, or the prepreg according to claim 9. The laminated board characterized by becoming.