TWI666248B - Maleimide resin composition, prepreg, laminate and printed circuit board - Google Patents

Abstract

The present invention relates to a maleimide imine resin composition and a prepreg, a laminate, and a printed circuit board using the same. The maleimide imine resin composition of the present invention comprises: a maleimide compound (A) having a structure of formula (I); an imidazole compound (B) having a structure of general formula (II); and an epoxy resin (C) ; And thermosetting resin (D).

Description

Maleimide resin composition, prepreg, laminate and printed circuit board

The invention relates to the technical field of electronic products, and in particular, to a maleimide resin composition which can be used as an insulating layer material of a printed circuit board, and a prepreg, a laminated board, and a printed circuit board using the same.

With the development of miniaturization, weight reduction, and multifunctionalization of semiconductor packages widely used in electronic devices, the form has been accelerated toward high integration and high-density mounting. Following this, the requirements for multilayer printed wiring boards also involve multiple aspects. From the perspective of environmental issues, there are demands for standardized flame retardance and high heat resistance based on halogen-free, phosphorus-free, and lead-free.

In general, in order to impart flame retardancy to a laminate, a halogen-based flame retardant or a phosphorus-based flame retardant may be used in combination. However, a halogen-based compound or a phosphorus-based compound is liable to generate a toxic compound during combustion. In order to respond to the currently exacerbated environmental problems, it is desired to realize a laminate having good flame retardancy without using a halogen-based compound or a phosphorus-based compound. As another method for improving the flame retardancy, a conventional example has disclosed an example in which a large amount of an inorganic filler is used in combination with a semiconductor packaging material. However, in order to produce flame retardancy, it is necessary to fill a large amount of inorganic filler, and the performance of resin flowability and drilling processability is very poor.

In addition, in order to reduce the size and density of the multilayer printed wiring board, research into reducing the thickness of the multilayer board used in the multilayer printed wiring board has been actively conducted. With thinning, due to In the manufacturing process of the printed circuit board, it is necessary to heat it to 260 ° C or higher by reflow soldering. If the glass transition temperature of the laminate is low, the thermal expansion in the plane direction between the laminate and the sealing resin will be caused by the aforementioned decrease in the thermal expansion coefficient. Increasing the difference in coefficients causes problems such as a decrease in mounting reliability and an increase in warpage of the multilayer printed wiring board. Therefore, a resin composition that is a material for a laminate is required to have a low thermal expansion coefficient and a high glass transition temperature.

As a method for increasing the glass transition temperature of a laminate, there is a method of using a component having a high glass transition temperature in a resin composition for a laminate, such as using maleimide having more functional group structure and larger molecular space. Resin, but this easily results in poor processability of the laminate molding.

In addition, as another method, a common method is to use a blend of a cyanate resin and bismaleimide. As the cyanate ester compound, a novolak-type cyanate resin is generally used. However, the curing conditions of novolac-type cyanate resins are extremely extreme, and under normal conditions, they tend to be insufficiently cured, and there is a problem that the cured product obtained has a large water absorption rate.

An object of the present invention is to provide a printed circuit that achieves good flame retardancy, low water absorption, and can be cured at a common temperature, achieves a high glass transition temperature, and has a high elastic modulus at high temperatures by being halogen-free and phosphorus-free. A resin composition for a board, a prepreg using the resin composition, and a laminate (including a metal foil-clad laminate) and a printed circuit board using the prepreg.

The present invention has been studied in order to solve the above problems, and as a result, it has been found that, as a resin composition for a printed circuit board, by using a maleimide compound having a specific structure, an imidazole compound having a specific structure, an epoxy resin, and a thermosetting resin, The obtained metal foil-clad laminate was excellent in flame retardancy, low water absorption, high glass transition temperature, and excellent peel strength. Thus, the present invention has been completed.

Specifically, the present invention includes the following technical solutions.

1. A maleimide imine resin composition, characterized in that the maleimide imine resin composition comprises: a maleimide compound (A) having a structure of formula (I); and a formula (II) ) Structure imidazole compound (B); epoxy resin (C); and thermosetting resin (D),

In formula (I), R is Group, hydrogen atom, alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 18 carbon atoms or aralkyl group having 7 to 24 carbon atoms, and R ₁ is an arylene group having 6 to 18 carbon atoms R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 24 carbon atoms, and n is 1 to 20 Integer

In the formula (II), Ar is a phenyl group, a naphthyl group, a biphenyl group, or a hydroxy substituent thereof; R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a carbon number 6 ~ 18 aryl groups or their hydroxy substituents, with the proviso that at least one of R ₄ and R ₅ is phenyl, naphthyl, biphenyl or their hydroxy substituents, or at least one is a carbon atom having a hydroxy substituent An alkyl group having 1 to 6 or an aryl group having 6 to 18 carbon atoms having a hydroxy substituent.

2. The maleimide imide resin composition according to 1, wherein in the maleimide imine compound (A) having the formula (I), n is an integer of 1 to 15, and preferably n Is an integer from 1 to 10; preferably, R is A group or a hydrogen atom; preferably, R ₁ is a phenylene group, a naphthylene group or a biphenylene group, further preferably R ₁ is a biphenylene group; preferably, R ₂ and R ₃ are hydrogen atoms.

3. The maleimide resin composition according to 1 or 2, wherein the epoxy resin (C) is selected from the group consisting of a novolac epoxy resin, a cresol novolac epoxy resin, and naphthol At least one of a phenolic epoxy resin, an anthracene epoxy resin, a phenolphthalein epoxy resin, an aralkylphenol novolac epoxy resin, and an epoxy resin containing an arylene ether structure in the molecule.

4. The maleimide imide resin composition according to any one of 1 to 3, wherein the thermosetting resin (D) is selected from the group consisting of a phenol resin, a cyanate resin, an acid anhydride compound, and styrene-maleic anhydride. At least one of a copolymer resin, an active ester resin, a benzoxazine resin, a polyphenylene ether resin, a silicone resin, an amine compound, and a dicyclopentadiene resin.

5. The maleimide imine resin composition according to any one of 1 to 4, wherein the maleimide imine resin composition further includes an inorganic filler (E), and the inorganic filler (E) is preferably It is at least one selected from the group consisting of silica, boehmite, alumina, magnesium hydroxide, and talc.

6. The maleimide imine resin composition according to any one of 1 to 5, wherein the maleimide resin (A), epoxy resin (C), and thermosetting resin (D) A total of 100 parts by mass, the content of the maleimide resin (A) is 10 to 80 parts by mass; the content of the imidazole compound (B) is 0.01 to 10 parts by mass; the epoxy resin (C) The content of 10 to 70 parts by mass; the content of the thermosetting resin (D) is 1 to 70 parts by mass; preferably, when an inorganic filler (E) is contained, it is relative to the maleimide resin (A) The total amount of the epoxy resin (C) and the thermosetting resin (D) is 100 parts by mass, and the content of the inorganic filler (E) is 10 to 400 parts by mass.

7. A prepreg, characterized in that the prepreg comprises a base material and the maleimide imine resin composition according to any one of 1 to 6 attached to the base material after impregnation and drying.

8. A laminate, characterized in that the laminate comprises at least one prepreg as described in 7.

9. The laminate according to 8, characterized in that the laminate is a metal foil-clad laminate, and the metal foil-clad laminate includes at least one prepreg as described in 7 and a prepreg Metal foil on one or both sides.

10. A printed circuit board, characterized in that the printed circuit board comprises at least one prepreg according to 7.

The maleimide imide resin composition of the present invention is a thermosetting resin composition, which can form a resin varnish having good storage stability, and a prepreg obtained by impregnating or coating the resin varnish has good curability, and High temperature and long time treatment is not required during curing, and the resulting layer The platen is excellent in chemical resistance and heat resistance. At the same time, the metal-clad laminate obtained from this prepreg has the characteristics of excellent flame retardancy, low water absorption, high glass transition temperature, and excellent peel strength. It is especially suitable for printed circuits that require high heat resistance and high reliability. Materials for boards.

Hereinafter, specific embodiments of the present invention will be described. It should be noted that the following embodiments are examples for explaining the present invention, and the present invention is not limited to these embodiments.

Resin composition

The resin composition of the present invention includes a specific maleimide compound (A), a specific imidazole compound (B), an epoxy resin (C), a thermosetting resin (D), an optional inorganic filler (E), and Solvent (F) and so on. Each component is described in detail below.

Maleimide compound (A)

The maleimide compound (A) having an unsaturated maleimide group used in the present invention is represented by the following general formula (I), and the method for synthesizing the maleimide compound (A) is not particularly limited. Those skilled in the art can choose according to the existing technology and their own professional knowledge. Specifically, for example, it can be obtained by reacting maleic anhydride with an amine compound having at least two primary amine groups in one molecule. This reaction is preferably performed in an organic solvent. An example of a product is MIR-3000 manufactured by Nippon Kayaku Co., Ltd. Since the compound has a biphenyl structure, the cured product has excellent flame retardancy. At the same time, the compound has a similar structure of novolac and has a large number of crosslinking points, which can effectively increase the glass transition temperature of the cured product.

In formula (I), R is Group, hydrogen atom, alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 18 carbon atoms or aralkyl group having 7 to 24 carbon atoms, and R ₁ is an arylene group having 6 to 18 carbon atoms R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 24 carbon atoms, and n is 1 to 20 Integer.

Preferably, in the maleimide compound (A) having the structure of formula (I), n is an integer of 1 to 15, more preferably n is an integer of 1 to 10; preferably, R is A group or a hydrogen atom; preferably, R ₁ is a phenylene group, a naphthylene group or a biphenylene group, further preferably R ₁ is a biphenylene group; preferably, R ₂ and R ₃ are hydrogen atoms.

The content of the maleimide imine compound (A) is not particularly limited. From the viewpoints of glass transition temperature and water absorption, compared with the maleimide imine compound (A), epoxy resin (C), and thermosetting resin, The total of (D) is 100 parts by mass, preferably in the range of 10 to 80 parts by mass, and more preferably 20 to 60 parts by mass.

Imidazole compound (B)

The imidazole compound (B) used in the present invention is a compound having a structure represented by the general formula (II). By adding the imidazole compound (B) to the resin composition, the curing reaction of the resin composition can be promoted, and the glass transition temperature and easy-curability of the cured product can be improved. In addition, the elastic modulus of the cured product at high temperatures can also be increased.

In formula (II), Ar is a phenyl group, a naphthyl group, a biphenyl group, or a hydroxy substituent thereof, and R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and 6 carbon atoms. ~ 18 aryl groups or their hydroxy substituents, with the proviso that at least one of R ₄ and R ₅ is phenyl, naphthyl, biphenyl or their hydroxy substituents, or at least one is a carbon atom having a hydroxy substituent An alkyl group having 1 to 6 or an aryl group having 6 to 18 carbon atoms.

"Alkyl group having 1 to 6 carbon atoms or aryl group having 6 to 18 carbon atoms having a hydroxy substituent" means an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 18 carbon atoms further contains a hydroxyl group The substituent, for example, an alkyl group having 1 to 6 carbon atoms having a hydroxy substituent includes hydroxymethyl, hydroxyethyl, hydroxypropyl and the like, and hydroxymethyl is preferred.

As a specific example, the imidazole compound (B) may have a structure represented by the general formula (III):

In the formula (III), Ar is a phenyl group, a naphthyl group, a biphenyl group, or a hydroxy substituent thereof.

Preferably, the imidazole compound (B) is 4-hydroxymethyl-5-methyl-2-phenylimidazole or 2,4,5-triphenylimidazole.

The content of the imidazole compound (B) represented by the general formula (II) is not particularly limited. From the viewpoints of storage stability of the prepreg and formability during processing of the metal-clad laminate, it is relative to horses. The total amount of the lyme imine compound (A), the epoxy resin (C), and the thermosetting resin (D) is 100 parts by mass, preferably in the range of 0.01 to 10 parts by mass, and more preferably in the range of 0.1 to 5 parts by mass.

Epoxy resin (C)

The epoxy resin (C) according to the present invention is not particularly limited, and is selected from compounds containing at least two epoxy groups in the molecular structure, and may be selected from bisphenol A type epoxy resin and bisphenol F type epoxy resin. Resin, novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, tetramethyl bisphenol F epoxy resin, bisphenol M epoxy resin, bisphenol S ring Oxygen resin, bisphenol E epoxy resin, bisphenol P epoxy resin, trifunctional phenol epoxy resin, tetrafunctional phenol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, naphthol Phenolic epoxy resin, anthracene epoxy resin, phenolphthalein epoxy resin, phenoxy epoxy resin, norbornene epoxy resin, adamantane epoxy resin, fluorene epoxy resin, biphenyl epoxy resin Epoxy resin, dicyclopentadiene epoxy resin, dicyclopentadiene novolac epoxy resin, aralkyl epoxy resin, aralkyl novolac epoxy resin, ring containing an arylene ether structure in the molecule Oxygen resin, alicyclic epoxy resin, polyol epoxy resin, silicon-containing epoxy resin, nitrogen-containing epoxy resin Phosphorus containing epoxy resin, glycidyl amine epoxy resins, glycidyl ring Oxygen resin and so on. In order to improve the heat resistance and flame retardancy of the cyanate resin composition, the epoxy resin according to the present invention is more preferably a novolac epoxy resin, a cresol novolac epoxy resin, a naphthol epoxy resin, and naphthol. Phenolic epoxy resin, anthracene epoxy resin, phenolphthalein epoxy resin, biphenyl epoxy resin, aralkyl epoxy resin, aralkyl phenolic epoxy resin, arylene ether structure in the molecule Any one or a mixture of at least two of epoxy resins, particularly preferably novolac epoxy resin, cresol novolac epoxy resin, naphthol novolac epoxy resin, anthracene epoxy resin, phenolphthalein epoxy resin Any one of resins, aralkyl novolac epoxy resins, and epoxy resins containing an arylene ether structure in the molecule, or a mixture of at least two of them. The epoxy resin (C) may be used alone, or at least two epoxy resins (C) may be mixed and used as required.

The content of the epoxy resin (C) is not particularly limited. From the viewpoints of flame retardancy, glass transition temperature, water absorption, and elastic modulus, compared with the maleimide compound (A) and epoxy resin, The total amount of (C) and thermosetting resin (D) is 100 parts by mass, and the amount of the epoxy resin (C) is 10 to 70 parts by weight, preferably in the range of 20 to 60 parts by mass, and more preferably 20 to 50 parts by mass .

Thermosetting resin (D)

The thermosetting resin (D) may be selected from a phenol resin, a cyanate resin, an acid anhydride compound, a styrene-maleic anhydride copolymer resin, an active ester resin, a benzoxazine resin, a polyphenylene ether resin, and a silicone resin. At least one of amine compound and dicyclopentadiene resin.

The active ester resin is obtained by reacting a phenolic compound, a difunctional carboxylic acid aromatic compound or an acid halide connected with an alicyclic hydrocarbon structure and a monohydroxy compound. The amount of the difunctional carboxylic acid aromatic compound or acid halide is 1 mol, the amount of phenol compounds connected through the alicyclic hydrocarbon structure is 0.05 to 0.75 mol, and the amount of the monohydroxy compound is 0.25 to 0.95 mol. The active ester resin may include an active ester of the following structural formula:

In the formula, X is a benzene ring or a naphthalene ring, j is 0 or 1, k is 0 or 1, and n represents an average repeating unit of 0.25-1.25.

From the viewpoint of moldability and heat resistance, the thermosetting resin (D) is preferably a phenol resin, a cyanate resin, an acid anhydride compound, a styrene-maleic anhydride copolymer resin, an active ester resin, a benzoxazine resin, and an amine. Compound. From the viewpoint of flame retardancy and heat resistance, phenol resin, cyanate resin, and benzoxazine resin are particularly preferred.

As the phenol resin used in the present embodiment, any resin may be used as long as it has two or more phenolic hydroxyl groups in one molecule, and known materials can be appropriately used, and the type is not particularly limited. Specific examples thereof include cresol novolac-type phenol resin, naphthol aralkyl-type phenol resin, biphenylaralkyl-type phenol resin, aminoditriazine novolac-type phenol resin, and naphthalene-type phenol Resins, phenol novolac resins, alkylphenol novolac resins, bisphenol A novolac resins, dicyclopentadiene phenolic resins, Xylock phenolic resins, terpene modified phenolic resins, and polyvinyl phenols.

Among the above phenol resins, from the viewpoints of water absorption and heat resistance of the obtained cured product, cresol novolac type phenol resin, biphenylaralkyl type phenol resin, naphthol aralkyl type phenol resin, and amine are preferred. From the viewpoint of flame retardancy, a triphenylazine novolac-type phenol resin and a naphthalene-type phenol resin are more preferably a biphenylaralkyl-type phenol resin and a naphthol-aralkyl-type phenol resin.

The content of the thermosetting resin (D) is not particularly limited. From the viewpoints of flame retardancy, glass transition temperature, and water absorption, the content is higher than that of the maleimide compound (A) and epoxy resin (C). A total of 100 parts by mass with the thermosetting resin (D), the amount of the thermosetting resin (D) is 1 to 70 parts by weight, preferably in the range of 5 to 60 parts by mass, and more preferably 10 to 50 parts by mass.

Inorganic filler (E)

As the inorganic filler (E) used in the present invention, an inorganic filler generally used in a resin composition for a circuit board can be used, and examples thereof include natural silica, fused silica, amorphous silica, and hollow Silicon dioxide such as silicon dioxide, metal hydrates such as aluminum hydroxide, boehmite, magnesium hydroxide, molybdenum compounds such as molybdenum oxide, zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc , Calcined clay, calcined kaolin, calcined talc, mica, glass short fibers (glass fine powders such as E glass, D glass), hollow glass, spherical glass, etc., can be used singly or in combination of two or more. Among them, from the viewpoint of thermal expansion coefficient and flame resistance, silicas, boehmite, magnesium hydroxide, alumina, and talc are preferred, and boehmite and silica are more preferred. Further preferred is fused silica or / and boehmite. Among them, fused silica is preferred because it has a low thermal expansion coefficient and boehmite is excellent in flame retardancy and heat resistance. Spherical fused silica is more preferred. Spherical fused silica has characteristics such as a low thermal expansion coefficient and good dielectric properties, and also has good dispersibility and fluidity, so it is preferred.

The average particle diameter (D50) of the inorganic filler (E) is not particularly limited. From the viewpoint of improving the manufacturability of the prepreg, it is preferably 0.01 to 10.0 μm, more preferably 0.1 to 5.0 μm, and even more preferably 0.2 ~ 3.0μm.

The content of the inorganic filler (E) in the resin composition is not particularly limited. From the viewpoint of reducing the thermal expansion of the insulating layer and obtaining a high peeling strength, the content of the inorganic filler (E) is higher than that of the maleimide compound (A) and epoxy. The total of the resin (C) and the thermosetting resin (D) is 100 parts by mass, preferably 10 to 400 parts by mass, more preferably 30 to 300 parts by mass, and even more preferably 50 to 250 parts by mass. When two or more inorganic fillers (E) are used in combination, it is preferable that their total content satisfies the above ratio.

Solvent (F)

The resin composition of the present invention may further contain a solvent (F) to prepare a solvent-free resin composition (resin varnish) into a glue solution suitable for application or impregnation. As the solvent (F) that can be used in the present invention, as long as it can dissolve various resin components without separation during mixing, examples thereof include methanol, ethanol, ethylene glycol, acetone, methyl ethyl ketone, and methyl ethyl methyl ester. Ketone, cyclohexanone, toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, ethyl acetate, ethylene glycol methyl ester Ether (MC), propylene glycol methyl ether (PM), propylene glycol methyl ether acetate (PMA), and the like. One or more solvents can be used.

The content of the solvent (F) in the resin composition is not particularly limited. For example, the amount of the solvent (F) may be 5 to 50 parts by weight, for example, 10 to 100 parts by weight of the resin composition (excluding the solvent). 50, 20-50, 30-40 parts by weight and so on.

Other components

The resin composition of the present invention may further include other additives such as other curing accelerators, wetting and dispersing agents, silane coupling agents, leveling agents, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, Additives, colorants or lubricants. These various additives may be used alone or in combination of two or more. However, the resin composition of the present invention is preferably free of halogens or halides and phosphorus-containing compounds. The amount of other additives can be arbitrarily adjusted within a range in which the effects of the present invention are not lost.

The resin composition of the present invention can also be used in combination with a maleimide compound other than the maleimide compound (A) having a structure of the formula (I), as long as it does not damage the inherent properties of the maleimide resin composition. Performance is enough. They can be used alone or in combination as required.

The thermosetting resin composition of the present invention may further contain an auxiliary molybdenum compound in order to ensure the processability of the resin composition.

Examples of the molybdenum compound include molybdenum dioxide, zinc molybdate, ammonium molybdate, magnesium molybdate, calcium molybdate, barium molybdate, sodium molybdate, potassium molybdate, phosphoromolybdic acid, ammonium phosphomolybdate, and phosphorus Molybdenum oxides such as sodium molybdate, silicomolybdic acid and molybdic acid compounds, molybdenum boride, molybdenum disilicide, molybdenum nitride, molybdenum carbide and other molybdenum compounds. These can be used singly or in combination of two or more kinds.

Among these, zinc molybdate, calcium molybdate, and magnesium molybdate are preferable from the viewpoints of low toxicity, good effects of electrical insulation, and drillability. When zinc molybdate, calcium molybdate, and magnesium molybdate are used as the molybdenum compound, the resin composition can be dissolved by using these molybdenum compounds on talc, silicon dioxide, zinc oxide, calcium carbonate, magnesium hydroxide, and the like. Prevents sedimentation and dispersibility when varnished in organic solvents.

The content of the molybdenum compound is preferably 0.05 to 20% by mass of the entire resin composition, and more preferably 0.1 to 10% by mass.

Prepregs, laminates, metal foil laminates, and printed circuit boards

The prepreg, laminate, metal foil-clad laminate, and printed circuit board of the present invention are all formed using the resin composition described above.

Prepreg

The prepreg of the present invention includes a substrate and the above-mentioned maleimide resin composition adhered to the substrate after being impregnated and dried.

As the base material of the prepreg, a fibrous sheet-shaped reinforcing base material is preferable, and for example, a well-known material used for a laminate of various electrical insulating materials can be used. Examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass, organic fibers such as polyimide, polyester, and tetrafluoroethylene, and mixtures thereof. Although these substrates have shapes such as woven fabrics, non-woven fabrics, rovings, chopped felts, and surface felts, the materials and shapes can be selected according to the use and performance of the intended shaped product, and can be used alone or in combination as needed. 2 or more materials and shapes.

The thickness of the substrate (fiber sheet-shaped reinforcing substrate) is not particularly limited, and for example, about 0.03 to 0.5 mm can be used. In terms of heat resistance, moisture resistance, and processability, a surface-treated substrate such as a silane coupling agent or a substrate subjected to mechanical fiber opening treatment is preferred.

The adhesion amount of the resin composition to the substrate is preferably such that the resin content of the dried prepreg is 20 to 90% by mass. After being impregnated or applied to a substrate, the prepreg of the present invention can be obtained by heating and drying at a temperature of 100 to 200 ° C. for 1 to 30 minutes to make it semi-cured (B-staged).

Laminates, metal-clad laminates

The laminate of the present invention is a laminate formed using one or more of the aforementioned prepregs. For example, a laminate (metal foil-clad laminate) can be manufactured by laminating and forming 1 to 20 prepregs and using a structure in which metal foils such as copper and aluminum are arranged on one or both sides. The metal foil is not particularly limited as long as it is a material used for electrical insulation materials, and examples thereof include metal foils such as copper and aluminum. Among these, copper foil is preferred. In particular, electrolytic copper foil, rolled copper foil, and the like can be suitably used. The metal foil may be subjected to a known surface treatment such as nickel treatment or cobalt treatment. The thickness of the metal foil can be appropriately adjusted within a range suitable as a material for a printed circuit board, and is preferably 2 to 35 μm.

The forming conditions can be applied to laminates and multilayer boards for electrical insulation materials. For example, multi-stage stamping, multi-stage vacuum stamping, continuous forming, and autoclave forming machines can be used. The temperature is 100 to 250 ° C, the pressure is 2 to 100 kg / cm ² , Molding is performed under the conditions of a heating time of 0.1 to 5 hours.

In addition, the prepreg of the present invention and a wiring board for an inner layer may be combined and laminated to produce a multilayer board.

A printed circuit board

The printed circuit board of the present invention includes a laminate formed by laminating the prepreg, and the prepreg includes the resin composition.

The printed circuit board can be manufactured by using the prepreg or metal foil-clad laminate as a build-up material. That is, a printed circuit board is produced by using them as a build-up material, and the prepreg constitutes an insulating layer containing a resin composition.

Specifically, when a prepreg is used as a build-up material, the prepreg is surface-treated by a conventional method, and a wiring pattern (conductor layer) is formed by plating on the surface of the insulating layer, thereby obtaining a printed circuit board.

When a metal foil-clad laminate is used as a build-up material, after the metal foil of the metal-clad laminate is etched by a conventional method, a layer (insulating layer) made of a prepreg is surface-treated, and the insulation is plated on the insulation. A wiring pattern (conductor layer) is formed on the surface of the layer, so that a printed circuit board can be obtained.

When using a prepreg as a build-up material, a metal foil-clad laminate may be produced using the prepreg by the above-mentioned method for manufacturing a metal-clad laminate, and then a printed circuit board may be obtained by the above-mentioned method. Alternatively, when used as a material for a multilayer printed circuit board, a prepreg may be directly used as a build-up material.

Examples

Examples and comparative examples are listed below to describe this embodiment in detail, but this embodiment is not limited to these examples.

In addition, the performance measurement and evaluation of the copper-clad laminate obtained in each Example and the comparative example were performed with the following method. Each component in the examples and comparative examples of the present invention is calculated as a solid.

Copper clad laminate:

Heat resistance (glass transition temperature Tg: ℃)

Using the prepared circuit wiring board sample having a thickness of 0.8 mm, the surface copper foil was removed by etching, and the temperature was raised from 40 ° C to 350 ° C at 10 ° C per minute using a thermo-mechanical analysis device (TA2980 manufactured by TA Instruments). , Determine the glass transition temperature.

Hygroscopic heat resistance:

A sample of a copper-clad laminate having an insulation layer thickness of 0.8 mm was used to cut a 100 mm × 100 mm square, and then a sample was prepared by removing copper foil by etching. After treating this sample with a pressure cooker tester at 121 ° C. and 2 atm for 6 hours, the water absorption of the evaluation laminate was measured. Then, the sample was immersed in a solder bath at 288 ° C. for 300 seconds, and the appearance change was visually observed for abnormality. Three tests were performed, and for each one, the case where there was no abnormality was recorded as “pass”, and the case where bursting occurred was recorded as “fail”.

Flexural modulus of elasticity (200 ° C):

The flexural modulus of the material was measured using a universal material testing machine at a temperature of 200 ° C.

Peel strength: (PS: N / mm)

Using the produced copper-clad laminate sample with a thickness of 0.4 mm, the copper-plating peel strength (adhesive force) was measured three times in accordance with the IPC-TM-650 method (copper foil peel tester), and the average peel strength was determined.

Flame retardancy: evaluated according to UL94 vertical combustion test method.

Coefficient of thermal expansion in the plane direction (XY-CTE: ppm / ℃)

The copper-clad laminate samples prepared in the examples and comparative examples were etched away from the copper foil to obtain a size of 4 mm × 60 mm, and the thermal expansion coefficient of the samples in the plane direction was measured by thermomechanical analysis (TMA), where the test direction To measure the thermal expansion coefficient in the plane direction from 50 ° C to 130 ° C from the room temperature 25 ° C to 300 ° C at a heating rate of 10 ° C / min along the direction of the glass fiber warp, the thickness of the test sample was 0.1 mm.

Example 1

50 parts by mass of a maleimide compound having a structure of the general formula (I) (MIR-3000, manufactured by Nippon Kayaku Co., Ltd.) and 30 parts by mass of a phenol biphenylaralkyl type epoxy resin (NC-3000-H , Manufactured by Nippon Kayaku Co., Ltd.) and 20 parts by mass of a phenol biphenylaralkyl phenol resin (MEHC-7851-H, Meiwa Chemical Co., Ltd.) were dissolved and mixed with methyl ethyl ketone, and 150 parts by mass of spherical fused silica ( SC2500-SQ, manufactured by Admatechs Company Limited), 1.5 parts by weight of an epoxy silane coupling agent (Z-6040, supplied by Dow Corning), and 1 part by mass of an imidazole compound (2-benzene) having a structure represented by the general formula (II) Methyl-4-methyl-5hydroxymethylimidazole, 2P4MHZ-PW, manufactured by Shikoku Chemical Industry Co., Ltd.) to obtain a varnish. This varnish was diluted with methyl ethyl ketone, and an E glass cloth having a thickness of 0.1 mm was dip-coated, and dried at 155 ° C. for 5 minutes to obtain a prepreg having a resin content of 50% by mass. 1 sheet, 4 sheets, and 8 sheets of the above prepregs were laminated, and an electrolytic copper foil with a thickness of 18 μm was laminated on each side, and cured in a press for 2 hours, and the curing pressure was 45 Kg / cm ² , The curing temperature was 200 ° C., and a copper-clad laminate having a thickness of 0.1, 0.4, and 0.8 mm was obtained.

Example 2

1 part by mass of an imidazole compound (2,4,5-triphenylimidazole, manufactured by TCI Corporation) having a structure represented by the general formula (III) is used in place of 2-phenyl-4-methyl-5hydroxymethylimidazole, Other than that, it carried out similarly to Example 1, and obtained the copper-clad laminate.

Example 3

3 parts by mass of an imidazole compound (2,4,5-triphenylimidazole, manufactured by TCI Co., Ltd.) having a structure represented by the general formula (III) was used instead of 2-phenyl-4-methyl-5hydroxymethylimidazole, Other than that, it carried out similarly to Example 1, and obtained the copper-clad laminate.

Example 4

0.25 parts by mass of an imidazole compound (2-phenyl-4-methyl-5hydroxymethylimidazole, 2P4MHZ-PW, manufactured by Shikoku Chemical Industry Co., Ltd.) having a structure represented by the general formula (II) was used instead of 1 part by mass A copper-clad laminate was obtained in the same manner as in Example 1 except that 2-phenyl-4-methyl-5hydroxymethylimidazole was used.

Example 5

5 parts by mass of a polyphenylmethane polymaleimide compound (BMI-2300, manufactured by Yamato Chemical Co., Ltd.) and 45 parts by mass of a maleimide compound (MIR-3000, Japan) having a structure of general formula (I) were used Except that MIR-3000 was replaced by 50 parts by mass, a copper-clad laminate was obtained in the same manner as in Example 2.

Example 6

20 parts by mass of a maleimide compound having a structure of the general formula (I) (MIR-3000, manufactured by Nippon Kayaku Co., Ltd.) and 48 parts by mass of a phenol biphenylaralkyl-based epoxy resin (NC-3000-H , Manufactured by Nippon Kayaku Co., Ltd.) and 32 parts by mass of phenol biphenylaralkyl-type phenol resin (MEHC-7851-H, Meiwa Chemical Co., Ltd.) were dissolved and mixed with methyl ethyl ketone, and the same operation was performed as in Example 1. A copper-clad laminate was obtained.

Example 7

60 parts by mass of a maleimide compound having a structure of the general formula (I) (MIR-3000, manufactured by Nippon Kayaku Co., Ltd.) and 24 parts by mass of a phenol biphenylaralkyl type epoxy resin (NC-3000-H , Manufactured by Nippon Kayaku Co., Ltd.) and 16 parts by mass of phenol biphenylaralkyl-type phenol resin (MEHC-7851-H, Meiwa Chemical Co., Ltd.) were dissolved and mixed with methyl ethyl ketone, and the same operation was performed as in Example 1. A copper-clad laminate was obtained.

Example 8

20 parts by mass of a phenol biphenylaralkyl type epoxy resin (NC-3000-H, manufactured by Nippon Kayaku Co., Ltd.) and 10 parts by mass of a 4-functional naphthalene type epoxy resin (EPICLON EXA-4710, manufactured by DIC Corporation) A copper-clad laminate was obtained in the same manner as in Example 1 except that 30 parts by mass of NC-3000-H was used.

Example 9

A copper-clad laminate was obtained in the same manner as in Example 2 except that 20 parts by mass of a naphthol aralkyl-type phenol resin (SN485, manufactured by Nippon Steel Chemical Co., Ltd.) was used instead of MEHC-7851-H.

Example 10

Except that 20 parts by mass of a novolac-type cyanate resin (PRIMASET PT-30, manufactured by LONZA JAPAN INC.) Was used instead of MEHC-7851-H, and 0.02 parts by mass of zinc octoate was added, the same procedure as in Example 2 was performed. Copper clad laminate.

Example 11

15 parts by mass of a phenol biphenylaralkyl-type phenolic resin (MEHC-7851-H, Meiwa Chemical Co., Ltd.) and 5 parts by mass of a styrene-maleic anhydride copolymer (SMA EF-40, manufactured by Satoori, USA) were used instead. Except for 20 parts by mass of MEHC-7851-H, a copper-clad laminate was obtained in the same manner as in Example 1.

Example 12

15 parts by mass of a phenol biphenylaralkyl-type phenol resin (MEHC-7851-H, Meiwa Chemical Co., Ltd.) and 5 parts by mass of a dicyclopentadiene-type active ester (HPC-8000-65T, Japan DIC Corporation) were used instead of 20 A copper-clad laminate was obtained in the same manner as in Example 1 except for the part by mass of MEHC-7851-H.

Example 13

15 parts by mass of a phenol biphenylaralkyl-type phenol resin (MEHC-7851-H, Meiwa Chemical Co., Ltd.) and 5 parts by mass of a polyphenylene ether resin (SA90, manufactured by Sabic) were used instead of 20 parts by mass of MEHC-7851-H. Other than that, it carried out similarly to Example 1, and obtained the copper-clad laminate.

Example 14

Except that 200 parts by mass of spherical fused silica (SC2500-SQ, manufactured by Admatechs Company Limited) was used instead of 120 parts by mass of spherical fused silica (SC2500-SQ, manufactured by Admatechs Company Limited), the same procedure as in Example 1 was used. In the same manner, a copper-clad laminate was obtained.

Example 15

120 parts by mass of boehmite (A0H-60, manufactured by Nabaltec) and 5 parts by mass of molybdenum compound (Kemgard 501, manufactured by Sherwin Williams) were used instead of 120 parts by mass of spherical fused silica (SC2500-SQ, manufactured by Admatechs Company Limited), Other than that, it carried out similarly to Example 1, and obtained the copper-clad laminate.

Comparative Example 1

50 parts by mass of a maleimide compound having a structure of the general formula (I) (MIR-3000, manufactured by Nippon Kayaku Co., Ltd.) and 30 parts by mass of a phenol biphenylaralkyl type epoxy resin (NC-3000-H , Manufactured by Nippon Kayaku Co., Ltd.) and 20 parts by mass of a phenol biphenylaralkyl-type phenol resin (MEHC-7851-H, Meiwa Chemical Co., Ltd.) were dissolved and mixed with methyl ethyl ketone, and 150 parts by mass of spherical fused silica ( SC2500-SQ, manufactured by Admatechs Company Limited), 1.5 parts by weight of an epoxy silane coupling agent (Z-6040, supplied by Dow Corning), and 1 part by mass of 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Chemical Co., Ltd. Industry Co., Ltd.) to obtain varnish. Because the gelation time of the resin varnish is too short, it does not have the technical ability to make a copper-clad laminate.

Comparative Example 2

In addition to using 0.25 parts by mass of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Chemical Industry Co., Ltd.) instead of 0.25 parts by mass of 2-phenyl-4-methyl-5hydroxymethylimidazole, and In the same manner as in Example 4, a copper-clad laminate was obtained.

Comparative Example 3

Except having used 0.25 parts by mass of 2-phenylimidazole (2PZ, manufactured by Shikoku Chemical Industry Co., Ltd.) instead of 0.25 parts by mass of 2-phenyl-4-methyl-5hydroxymethylimidazole, it was carried out in the same manner as in Example 4. This operation gave a copper-clad laminate.

Comparative Example 4

Except that 2-phenyl-4-methylimidazole (2P4MZ, manufactured by Shikoku Chemical Industry Co., Ltd.) was used instead of 0.25 parts by mass of 2-phenyl-4-methyl-5hydroxymethylimidazole, it was the same as in Example 4 In the same manner, a copper-clad laminate was obtained.

Comparative Example 5

0.25 parts by mass of 2,4-diamino-6- [2'-ethyl-4'-methylimidazolinyl- (1) ']-ethyl-s-triazine (2E4MZ-A, Shikoku Chemical Co., Ltd. Industry Co., Ltd.), except that 0.25 parts by mass of 2-phenyl-4-methyl-5hydroxymethylimidazole was replaced, in the same manner as in Example 4, a copper-clad laminate was obtained.

Comparative Example 6

0.25 parts by mass of 2,4-diamino-6- [2'-undecylimidazolinyl- (1) ']-ethyl-triazine (C11Z-A, manufactured by Shikoku Chemical Industries, Ltd. ) A copper-clad laminate was obtained in the same manner as in Example 4 except that 0.25 parts by mass of 2-phenyl-4-methyl-5hydroxymethylimidazole was replaced.

Comparative Example 7

50 parts by mass of a polyphenylmethane polymaleimide compound (BMI-2300, manufactured by Yamato Chemical Co., Ltd.) and 30 parts by mass of a phenol biphenylaralkyl-based epoxy resin (NC-3000-H, Nippon Kayaku) Co., Ltd.) and 20 parts by mass of a phenol biphenylaralkyl-type phenol resin (MEHC-7851-H, Meiwa Chemical Co., Ltd.) were dissolved and mixed with methyl ethyl ketone, and 150 parts by mass of spherical fused silica (SC2500-SQ, Admatechs Company Limited), 1.5 parts by weight of epoxy silane coupling agent (Z-6040, supplied by Dow Corning), and 1 part by mass of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Chemical Industries, Ltd.) ) To get varnish. Because a large amount of solvent is required to dissolve 50 parts by mass of the polyphenylmethane polymaleimide compound, the solid content of the resin varnish is too low, and it does not have the processability for making a copper-clad laminate.

Comparative Example 8

20 parts by mass of a polyphenylmethane polymaleimide compound (BMI-2300, manufactured by Yamato Chemical Co., Ltd.) was used in place of 20 parts by mass of a maleimide compound having a structure of general formula (I) (MIR-3000, Japan Except having manufactured by Kayaku Co., Ltd., it carried out similarly to Example 6, and obtained the copper-clad laminate.

Comparative Example 9

20 parts by mass of a bis (3-ethyl-5-methyl-4-maleiminobenzene) methane compound (BMI-70, manufactured by KI Kasei Co., Ltd.) was used instead of 20 parts by mass as shown in the general formula ( I) A maleimide compound (MIR-3000, manufactured by Nippon Kayaku Co., Ltd.) was used in the same manner as in Example 6 to obtain a copper-clad laminate.

Comparative Example 10

20 parts by mass of 2,2'-bis [4- (4-maleiminophenoxy) phenyl] propane compound (BMI-80, manufactured by KI Kasei Co., Ltd.) is used instead of A copper-clad laminate was obtained in the same manner as in Example 6 except that the maleimide compound (MIR-3000, manufactured by Nippon Kayaku Co., Ltd.) having the general formula (I) was used.

Comparative Example 11

Using a prepreg obtained by the same manufacturing method as Comparative Example 9, one sheet, four sheets, and eight sheets of prepreg were laminated, and an electrolytic copper foil with a thickness of 18 μm was laminated on each of the two sides. Curing was performed in the machine for 2 hours, the curing pressure was 45 Kg / cm ² , the curing temperature was 220 ° C., and a copper-clad laminate having a thickness of 0.1, 0.4, and 0.8 mm was obtained.

Comparative Example 12

Using a prepreg obtained by the same manufacturing method as Comparative Example 10, one sheet, four sheets, and eight sheets of prepreg were laminated, and an electrolytic copper foil with a thickness of 18 μm was laminated on each of the two sides. Curing was performed in the machine for 2 hours, the curing pressure was 45 Kg / cm ² , the curing temperature was 220 ° C., and a copper-clad laminate having a thickness of 0.1, 0.4, and 0.8 mm was obtained.

The glass-clad laminates prepared in the above-mentioned Examples 1-15 and Comparative Examples 1-12 according to the measurement methods described above, with respect to glass transition temperature (° C), peel strength (N / mm), and water absorption (%) , Moisture absorption heat resistance (pass is pass / fail is not pass), flexural modulus (GPa) at high temperature (200 ° C), thermal expansion coefficient in the plane direction (CTE: ppm / ° C) and flame retardancy are tested, and the specific results show In Table 1 below.

In Comparative Example 1, when the same amount of imidazole compound as in Example 1 was added and the structure was inconsistent, the gelation time was too short, so the processability was not provided. Comparative Example 7 was added with the same amount of maleimide as in Example 1 and the structure was not consistent. In the case of compounds, because the varnish solid content is too low, the processability is not available, When the solid content is appropriate, there is a problem that the maleimide compound cannot be completely dissolved, and it is not processable.

The difference between Comparative Example 2-6 and Example 1-4 is that the imidazole compound is different. Example 1-4 uses the imidazole compound of the present invention, while Comparative Example 2-6 uses an imidazole compound different from the present invention. The former has obvious advantages. The latter has a glass transition temperature (Tg) and a water absorption rate; the difference between Comparative Examples 8-10 and Example 6 is that the maleimide compound is different. When the maleimide compound of formula I is not used (comparative example) 8-10), the flame retardancy and moisture absorption heat resistance are poor, and the water absorption rate is significantly higher.

Compared with the comparative example, the maleimide imide resin composition of the present invention is more easily cured completely, and has higher heat resistance, mechanical properties and lower water absorption at the same curing temperature, without using the malein of the present invention. In the comparative examples of the fluorene imine resin composition, even when cured at a higher curing temperature (Comparative Examples 11-12), the characteristics of high heat resistance, mechanical properties, and low water absorption of the present invention cannot be achieved.

The above are only some embodiments of the present invention. For those of ordinary skill in the art, various other corresponding changes and modifications can be made according to the technical solutions and technical concepts of the present invention, and all these changes and modifications should belong to The scope of patent application scope of the present invention.

The present invention illustrates the detailed method of the present invention through the foregoing embodiments, but the present invention is not limited to the detailed method, which does not mean that the present invention must rely on the detailed method to be implemented. Those skilled in the art should know that any improvement to the present invention, equivalent replacement of the raw materials of the products of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.

Claims (10)

A maleimide imine resin composition, characterized in that the maleimide imine resin composition includes: a maleimide compound (A) having a structure of formula (I); and a structure having a general formula (II). Imidazole compound (B); epoxy resin (C); and thermosetting resin (D), In formula (I), R is Group, hydrogen atom, alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 18 carbon atoms or aralkyl group having 7 to 24 carbon atoms, and R ₁ is an arylene group having 6 to 18 carbon atoms R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms or an aralkyl group having 7 to 24 carbon atoms, and n is 1 to 20 Integer In formula (II), Ar is a phenyl group, a naphthyl group, a biphenyl group, or a hydroxy substituent thereof; R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a carbon number 6 ~ 18 aryl groups or their hydroxy substituents, with the proviso that at least one of R ₄ and R ₅ is a phenyl, naphthyl, biphenyl or their hydroxy substituent, or at least one is a carbon atom having a hydroxy substituent An alkyl group having 1 to 6 or an aryl group having 6 to 18 carbon atoms having a hydroxy substituent; wherein the maleimide resin (A), epoxy resin (C), and thermosetting resin (D) A total of 100 parts by mass, the content of the maleimide resin (A) is 10 to 80 parts by mass; the content of the imidazole compound (B) is 0.01 to 10 parts by mass; the epoxy resin (C) The content of is from 10 to 70 parts by mass; the content of the thermosetting resin (D) is from 1 to 70 parts by mass. The maleimide imine resin composition according to claim 1, wherein in the maleimide imine compound (A) having the structure of the formula (I), R ₁ is a phenylene group, a naphthylene group, or a propylene group Phenyl. The maleimide imide resin composition according to claim 1, wherein the epoxy resin (C) is selected from the group consisting of a novolac epoxy resin, a cresol novolac epoxy resin, and a naphthol novolac epoxy resin. At least one of anthracene-type epoxy resin, phenolphthalein-type epoxy resin, aralkyl novolac-type epoxy resin, and epoxy resin containing an arylene ether structure in the molecule. The maleimide imide resin composition according to claim 1, wherein the thermosetting resin (D) is selected from a phenol resin, a cyanate resin, an acid anhydride compound, a styrene-maleic anhydride copolymer resin, an active ester resin, At least one of a benzoxazine resin, a polyphenylene ether resin, a silicone resin, an amine compound, and a dicyclopentadiene resin. The maleimide imide resin composition according to claim 1, wherein the maleimide imide resin composition further includes an inorganic filler (E). The maleimide imine resin composition according to claim 5, which is inorganic based on 100 parts by mass of a total of the maleimide resin (A), the epoxy resin (C), and the thermosetting resin (D). The content of the filler (E) is 10 to 400 parts by mass. A prepreg, characterized in that the prepreg comprises a substrate and the maleimide imide resin composition according to any one of claims 1 to 6 attached to the substrate after impregnation and drying. A laminate, characterized in that the laminate includes at least one prepreg according to claim 7. The laminate according to claim 8, wherein the laminate is a metal foil-clad laminate, and the metal foil-clad laminate includes at least one prepreg according to claim 7 and is covered on one side of the prepreg Or metal foil on both sides. A printed circuit board, characterized in that the printed circuit board comprises at least one prepreg according to claim 7.