WO2019127391A1

WO2019127391A1 - Maleimide resin composition, prepreg, laminate and printed circuit board

Info

Publication number: WO2019127391A1
Application number: PCT/CN2017/119906
Authority: WO
Inventors: 李鸿杰; 唐军旗
Original assignee: 广东生益科技股份有限公司
Priority date: 2017-12-29
Filing date: 2017-12-29
Publication date: 2019-07-04
Also published as: KR20200060498A; KR102325101B1

Abstract

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

Description

Maleimide resin composition, prepreg, laminate and printed circuit board

Technical field

The present invention relates to the field of electronic product technology, and in particular to a maleimide resin composition useful as an insulating layer material for a printed circuit board, and a prepreg, a laminate, and a printed circuit board using the same.

Background technique

With the development of miniaturization, weight reduction, and multi-functionality of semiconductor packages widely used in electronic devices and the like, the form is also accelerating toward high integration and high-density mounting. Accordingly, the requirements for multilayer printed wiring boards also involve various aspects. From the consideration of environmental issues, it is required to be based on halogen-free, phosphorus-free, lead-free, standardized flame retardancy, high heat resistance, and the like. characteristic.

In general, in order to impart flame retardancy to the laminate, a halogen-based flame retardant or a phosphorus-based flame retardant may be used in combination, however, a halogen compound or a phosphorus-based compound is likely to generate a toxic compound upon burning. In order to comply with the environmental problems that are currently intensified, it is desirable to realize a laminate which still has good flame retardancy without using a halogen compound or a phosphorus compound. As another method for improving flame retardancy, in the conventional example, an example in which a large amount of inorganic filler is used in combination with a semiconductor encapsulating material is disclosed. However, in order to produce flame retardancy, it is necessary to fill a large amount of inorganic filler, and the performance in terms of resin fluidity and drilling processability is very poor.

In addition, since the multilayer printed wiring board has been reduced in size and density, research into thinning a laminated board used in a multilayer printed wiring board has been actively conducted. With the thinning, since the reflow soldering process needs to be heated to 260 ° C or higher in the manufacturing process of the printed wiring board, if the glass transition temperature of the laminate is low, the laminate and the encapsulating resin are caused by the decrease in the thermal expansion coefficient. The increase in the difference in the coefficient of thermal expansion between the faces in the surface direction causes a problem that the mounting reliability is lowered and the warpage of the multilayer printed circuit board is increased. Therefore, the resin composition which is a material of the laminate requires a low thermal expansion coefficient and a high glass transition. temperature.

As a method of 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 a maleimide having a more functional group structure and a larger molecular space type. Resin, but this is likely to result in poor lamination processability.

Also as a further method, a common method is to use a blend of a cyanate resin and a bismaleimide. As the cyanate ester compound, a novolac type cyanate resin is usually used. However, the curing conditions of the novolac type cyanate resin are extremely extreme, and it is easy to cure under normal conditions, and there is a problem that the obtained cured product has a large water absorption rate.

Summary of the invention

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

In order to solve the above problems, the present invention has been found to provide, as a resin composition for a printed circuit board, 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 is excellent in flame retardancy, low water absorption, high glass transition temperature, and peel strength. The present invention has thus been completed.

Specifically, the present invention includes the following technical solutions.

A maleimide resin composition, characterized in that the maleimide resin composition comprises:

a maleimide compound (A) having the structure of formula (I);

An imidazole compound (B) having the structure of the formula (II);

Epoxy resin (C); and

Thermosetting resin (D),

In formula (I), R is

a group, 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 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 carbon atoms. Integer

In the formula (II), Ar is a phenyl group, a naphthyl group, a biphenyl group or a hydroxy group 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; Aryl groups of -18 or their hydroxy substitutions, provided that at least one of R ₄ and R ₅ is phenyl, naphthyl, biphenyl or a hydroxy substituent thereof, or at least one carbon atom having a hydroxy substituent An alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 18 carbon atoms having a hydroxy substituent.

2. The maleimide resin composition according to 1, wherein, in the maleimide compound (A) having the structure of the formula (I), n is an integer of from 1 to 15, preferably n. 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 biphenylylene group, and further preferably R1 is a biphenylylene group;

Preferably, R ₂ and R ₃ are a hydrogen atom.

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

4. The maleimide 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. Copolymer resin, active ester resin, benzoxazine resin, polyphenylene ether resin, silicone resin, amine compound, dicyclopentadiene resin and copolymerization with epoxy resin and/or maleimide resin At least one of the compounds.

5. The maleimide resin composition according to any one of 1 to 4, wherein the maleimide resin composition further comprises 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 resin composition according to any one of 1 to 5, which is characterized in that, relative to said maleimide resin (A), epoxy resin (C) and thermosetting resin (D) 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 the thermosetting resin (D) is from 1 to 70 parts by mass; preferably, when the inorganic filler (E) is contained, 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.

A prepreg comprising a substrate and a maleimide resin composition as described in any one of 1 to 6 which is adhered to the substrate after impregnation and drying.

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

The laminate according to claim 8, wherein said laminate is a metal foil laminate, said metal foil laminate comprising at least one prepreg as described in 7, and overlying prepreg A metal foil on one or both sides of the material.

10. A printed wiring board, characterized in that said printed wiring board comprises at least one prepreg as described in 7.

The maleimide 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 with a resin varnish has good curability. Moreover, high temperature and long-time treatment are not required at the time of curing, and the obtained laminate is excellent in chemical resistance and heat resistance. At the same time, the metal foil-clad laminate obtained by the prepreg has the characteristics of excellent flame retardancy, low water absorption, high glass transition temperature and excellent peel strength, and is particularly suitable for printing requiring high heat resistance and high reliability. Materials for circuit boards.

Detailed ways

Hereinafter, specific embodiments of the present invention will be described. It is to be noted that the following embodiments are illustrative of the invention, and the invention is not limited to the embodiments.

-Resin composition -

The resin composition of the present invention comprises 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), etc. The individual components are 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 formula (I), and the method for synthesizing the maleimide compound (A) is not particularly limited. Those skilled in the art can make their own choices according to the prior art in combination with their own expertise. Specifically, for example, it can be obtained by reacting maleic anhydride with an amine compound having at least two primary amino groups in one molecule. This reaction is preferably carried out in an organic solvent. As an example of the product, there is MIR-3000 manufactured by Nippon Kayaku Co., Ltd. Since the compound has a biphenyl structure, the cured product is excellent in flame retardancy, and the compound has a similar structure of a novolac and a large number of crosslinking points, so that the glass transition temperature of the cured product can be effectively increased.

In formula (I), R is

a group, 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 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 carbon atoms. Integer.

Preferably, in the maleimide compound (A) having a structure of the formula (I), n is an integer of from 1 to 15, more preferably n is an integer of from 1 to 10;

Preferably, R is

a group or a hydrogen atom;

Preferably, R ₂ and R ₃ are a hydrogen atom.

The content of the maleimide compound (A) is not particularly limited, and is relative to the maleimide compound (A), the epoxy resin (C), and the thermosetting property from the viewpoints of glass transition temperature and water absorption. The total amount of the resin resin (D) is 100 parts by mass, preferably 10 to 80 parts by mass, 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 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 the curability of the cured product can be improved. In addition, the elastic modulus of the cured product at a high temperature can also be increased.

In the formula (II), Ar is a phenyl group, a naphthyl group, a biphenyl group or a hydroxy group thereof, and each of R ₄ and R _{5 is} independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and 6 carbon atoms. Aryl groups of -18 or their hydroxy substitutions, provided that at least one of R ₄ and R ₅ is phenyl, naphthyl, biphenyl or a hydroxy substituent thereof, or at least one carbon atom having a hydroxy substituent An alkyl group having 1 to 6 or an aryl group having 6 to 18 carbon atoms.

The "alkyl group having 1 to 6 carbon atoms or the aryl group having 6 to 18 carbon atoms having a hydroxy substituent" means that the alkyl group having 1 to 6 carbon atoms or the 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 a methylol group, a hydroxyethyl group, a hydroxypropyl group or the like, and a hydroxymethyl group 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 group 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 formula (II) is not particularly limited, and is relative to the horse from the viewpoint of storage stability of the prepreg and formability at the time of processing of the metal foil-clad laminate. The total mass of the imide compound (A), the epoxy resin (C), and the thermosetting resin (D) is 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 having at least two epoxy groups in a molecular structure, and may be selected from bisphenol A type epoxy resins and bisphenol F type epoxy resins. Resin, novolac epoxy resin, cresol novolac epoxy resin, bisphenol A phenolic epoxy resin, tetramethyl bisphenol F epoxy resin, bisphenol M epoxy resin, bisphenol S ring Oxygen resin, bisphenol E type epoxy resin, bisphenol P type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, naphthol Phenolic epoxy resin, fluorene epoxy resin, phenolphthalein epoxy resin, phenoxy epoxy resin, norbornene epoxy resin, adamantane epoxy resin, fluorene epoxy resin, biphenyl type Epoxy resin, dicyclopentadiene type epoxy resin, dicyclopentadiene novolac type epoxy resin, aralkyl type epoxy resin, aralkyl novolac type epoxy resin, ring containing arylene ether structure in the molecule Oxygen resin, cycloaliphatic epoxy resin, polyol epoxy resin, silicon-containing epoxy resin, nitrogen-containing epoxy resin Phosphorus containing epoxy resin, glycidyl amine epoxy resins, glycidyl ester epoxy resin. In order to improve the heat resistance and flame retardancy of the cyanate resin composition, the epoxy resin according to the present invention is further preferably a novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthol type epoxy resin, or a naphthalene. Phenolic novolac type epoxy resin, bismuth type epoxy resin, phenolphthalein type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, aralkyl phenolic type epoxy resin, arylene ether in molecule Any one of the structural epoxy resins or a mixture of at least two, particularly preferably a novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthol novolac type epoxy resin, a fluorene type epoxy resin, a phenolphthalein type Any one or a mixture of at least two of an epoxy resin, an aralkyl novolac type epoxy resin, and an epoxy resin having an arylene ether structure in its molecule. The epoxy resin (C) may be used singly or in combination of at least two types of epoxy resins (C) as needed.

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

Thermosetting resin (D)

The thermosetting resin (D) may be selected from the group consisting of 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 an amine compound, a dicyclopentadiene resin, and a compound which can be copolymerized with an epoxy resin and/or a maleimide resin.

The active ester resin is obtained by reacting a phenolic compound linked by an aliphatic cyclic hydrocarbon structure, a difunctional carboxylic acid aromatic compound or an acid halide, and a monohydroxy compound. The amount of the difunctional carboxylic acid aromatic compound or acid halide is 1 mol, the amount of the phenolic compound linked by the aliphatic cyclic 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 comprise an active ester of the formula:

Wherein X is a benzene or naphthalene ring, j is 0 or 1, k is 0 or 1, and n represents an average repeating unit of 0.25 to 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, or an amine. Class of compounds. Further, from the viewpoints of flame retardancy and heat resistance, a phenol resin, a cyanate resin, and a benzoxazine resin are particularly preferable.

The phenol resin used in the present embodiment may be any resin having two or more phenolic hydroxyl groups in one molecule, and a known one may be appropriately used, and the type thereof is not particularly limited. Specific examples thereof include a cresol novolac type phenol resin, a naphthol aralkyl type phenol resin, a biphenyl aralkyl type phenol resin, an aminoditriazine novolac type phenol resin, and a naphthol type phenol resin. A phenol novolak resin, an alkylphenol novolak resin, a bisphenol A novolak resin, a dicyclopentadiene type phenol resin, a Xylock type phenol resin, a terpene modified phenol resin, and a polyvinyl phenol.

The phenol resin is preferably a cresol novolak type phenol resin, a biphenyl aralkyl type phenol resin, a naphthol aralkyl type phenol resin, from the viewpoint of water absorbability and heat resistance of the obtained cured product. The aminotriazine novolac type phenol resin and the naphthalene type phenol resin are more preferably a biphenyl aralkyl type phenol resin or a naphthol aralkyl type phenol resin from the viewpoint of flame retardancy.

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

Inorganic filler (E)

As the inorganic filler (E) used in the present invention, an inorganic filler generally used for a resin composition for a circuit board can be used, and examples thereof include natural silica, fused silica, amorphous silica, and hollow. Silicas such as silica, metal hydrates such as aluminum hydroxide, boehmite, magnesium hydroxide, molybdenum compounds such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, alumina, clay, kaolin, talc The calcined clay, the calcined kaolin, the calcined talc, the mica, the glass short fibers (glass fine powder such as E glass or D glass), the hollow glass, the spherical glass, or the like, may be used alone or in combination of two or more. Among them, from the viewpoint of thermal expansion coefficient and flame resistance, silica, gangue, magnesium hydroxide, alumina, and talc are preferable, and boehmite and silica are more preferable. Further preferred is fused silica or/and boehmite. Among them, fused silica has a characteristic of a low coefficient of thermal expansion, and boehmite is preferred because it is excellent in flame retardancy and heat resistance. More preferably, spherical fused silica, which has characteristics such as a low coefficient of thermal expansion and good dielectric properties, has good dispersibility and fluidity, and is therefore preferred.

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

The content of the inorganic filler (E) in the resin composition is not particularly limited, and from the viewpoint of lowering thermal expansion of the insulating layer and obtaining high peel strength, relative to the maleimide compound (A), epoxy The total amount of the resin (C) and the thermosetting resin (D) is preferably 10 to 400% by mass, more preferably 30 to 300% by mass, still more preferably 50 to 250% by mass. In addition, when two or more types of 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) in a form suitable for coating or impregnation. The solvent (F) which can be used in the present invention is not particularly limited as long as it can dissolve various resin components and does not separate upon mixing, and examples thereof include methanol, ethanol, ethylene glycol, acetone, methyl ethyl ketone, and methyl ethyl group. Methyl ketone, cyclohexanone, toluene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, ethyl acetate, ethylene glycol methyl 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, and for example, the solvent (F) may be used in an amount of 5 to 50 parts by weight, for example, 10 parts by weight per 100 parts by weight of the resin composition (excluding the solvent). 50, 20-50, 30-40 parts by weight, and the like.

Other components

The resin composition of the present invention may further contain 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 singly or in combination of two or more kinds. However, the resin composition of the present invention preferably contains no halogen or halide and a phosphorus-containing compound. The amount of the other additives can be arbitrarily adjusted within the range not detracting from the effects of the present invention.

The resin composition of the present invention may 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 impair the inherentity of the maleimide resin composition. Performance can be. They can be used singly or in combination of plural kinds as needed.

In the thermosetting resin composition of the present invention, an auxiliary molybdenum compound may be contained 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, phosphomolybdic acid, ammonium phosphomolybdate, and phosphorus. Molybdenum oxide such as sodium molybdate or silicomolybdic acid, molybdenum acid compound, molybdenum boride, molybdenum disilide, molybdenum nitride or molybdenum carbide. One type of these may be used or two or more types may be used in combination.

Among them, zinc molybdate, calcium molybdate, and magnesium molybdate are preferred from the viewpoint of good effects of low toxicity, electrical insulation, and drilling processability. When zinc molybdate, calcium molybdate or magnesium molybdate is used as the molybdenum compound, the molybdenum compound can be used by being supported on talc, silica, zinc oxide, calcium carbonate, magnesium hydroxide or the like to dissolve the resin composition. Prevents sedimentation and dispersibility during organic solvent varnishing.

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

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

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

Prepreg

The prepreg of the present invention comprises a substrate and the above-described maleimide resin composition adhered to the substrate by impregnation and drying.

As the base material of the prepreg, a fiber sheet-shaped reinforcing base material is preferable, and for example, a well-known material used for various laminated sheets for electrical insulating materials can be used. Examples of the material thereof 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 base materials have a shape of, for example, a woven fabric, a nonwoven fabric, a roving, a chopped strand mat, and a surface felt, the material and shape can be selected according to the use and performance of the intended molded article, and can be individually or in combination as needed. Two 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. From the viewpoint of heat resistance, moisture resistance, and workability, a substrate surface-treated with a silane coupling agent or the like, or a substrate subjected to mechanical fiber opening treatment is preferable.

The amount of the resin composition to be adhered to the substrate is preferably 20 to 90% by mass based on the resin content of the dried prepreg. After immersion or application to a substrate, the prepreg of the present invention is obtained by heating and drying at a temperature of 100 to 200 ° C for 1 to 30 minutes to semi-cure (B-stage).

Laminate, metal foil laminate

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

The molding conditions can be applied to laminates and multilayer boards for electrical insulating materials, for example, multi-stage press, multi-stage vacuum press, continuous forming, autoclave molding machine, etc., at a temperature of 100 to 250 ° C and a pressure of 2 to 100 kg/cm ^{2 .} The molding is carried out under the conditions of a heating time of 0.1 to 5 hours.

Further, the prepreg and the inner layer wiring board of the present invention may be combined and laminated to form a multilayer board.

A printed circuit board

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

The printed circuit board can be produced by using the above prepreg or metal foil-clad laminate as a laminate 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 the prepreg is used as a laminate material, the prepreg is subjected to surface treatment by a conventional method, and a wiring pattern (conductor layer) is formed by plating on the surface of the insulating layer, whereby a printed circuit board can be obtained. .

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

When the prepreg is used as a laminate material, a metal foil-clad laminate can be produced by using the prepreg by the above-described method for producing a metal foil-clad laminate, and then a printed circuit board can be obtained by the above method. Alternatively, when used as a material for a multilayer printed circuit board, the prepreg can also be directly used as a laminate material.

Example

The embodiment will be described in detail below by way of examples and comparative examples, but the 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 by the following methods. In the examples and comparative examples of the present invention, each component was calculated as a solid matter.

Copper clad laminate:

Heat resistance (glass transition temperature Tg: °C)

Using a prepared circuit wiring board sample having an insulating layer 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 by a thermomechanical analyzer (TA 2980 manufactured by TA INSTRUMENTS LTD.). , the glass transition temperature was measured.

Moisture absorption heat resistance:

A copper clad laminate sample having a thickness of 0.8 mm was used, and after cutting into a 100 mm × 100 mm square, a sample obtained by etching the copper foil was prepared. The sample was treated with a pressure cooker at 121 ° C and 2 atm for 6 hours, and then the water absorption of the laminate was evaluated. 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 piece, the case where no abnormality was recorded was "pass", and the case where the bursting occurred was referred to as "fail".

Flexural modulus of elasticity (200 ° C):

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

Peel strength: (PS: N / mm)

Using the prepared copper foil laminate sample having an insulating layer thickness of 0.4 mm, the copper plating peel strength (adhesive strength) was measured three times according to the IPC-TM-650 method (copper foil peeling resistance meter), and the average value of the peeling strength was determined. .

Flame retardancy: evaluated according to the UL94 vertical burning test method.

Thermal expansion coefficient in the plane direction (XY-CTE: ppm/°C)

The copper foil laminate samples prepared in the examples and the comparative examples were etched away from the copper foil to have a size of 4 mm × 60 mm, and the thermal expansion coefficient (400A) of the sample was measured by a thermomechanical analysis method (TMA), wherein the test direction was measured. The coefficient of thermal expansion in the plane direction from 50 ° C to 130 ° C was measured in the direction of the warp of the glass fiber cloth at a temperature rising rate of 10 ° C / min from room temperature 25 ° C to 300 ° C. The thickness of the test sample was 0.1 mm.

Example 1

50 parts by mass of a maleimide compound (MIR-3000, manufactured by Nippon Kayaku Co., Ltd.) having a structure of the formula (I), and 30 parts by mass of a phenol biphenyl aralkyl type epoxy resin (NC-3000-H) 20 parts by mass of phenol biphenyl aralkyl phenol resin (MEHC-7851-H, Mingwa Kasei Co., Ltd.) was dissolved and mixed with methyl ethyl ketone, and 150 parts by mass of spherical fused silica (SC2500) was further mixed. -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-phenyl group) having a structure represented by the formula (II) -4-Methyl-5-hydroxymethylimidazole, 2P4MHZ-PW, manufactured by Shikoku Chemicals Co., Ltd., to obtain a varnish. The varnish was diluted with methyl ethyl ketone, and the E glass cloth having a thickness of 0.1 mm was dip-coated, and dried by heating at 155 ° C for 5 minutes to obtain a prepreg having a resin content of 50% by mass. One, four, and eight sheets of the above prepreg were laminated, and an electrolytic copper foil having a thickness of 18 μm was pressed on both sides thereof, and solidified 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 Co., Ltd.) having a structure represented by the formula (III) was used instead of 2-phenyl-4-methyl-5-hydroxymethylimidazole. A copper-clad laminate was obtained in the same manner as in Example 1 except the above.

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 formula (III) was used instead of 2-phenyl-4-methyl-5-hydroxymethylimidazole. A copper-clad laminate was obtained in the same manner as in Example 1 except the above.

Example 4

0.25 parts by mass of an imidazole compound (2-phenyl-4-methyl-5-hydroxymethylimidazole, 2P4MHZ-PW, manufactured by Shikoku Chemicals Co., Ltd.) having a structure represented by the 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 -phenyl-4-methyl-5-hydroxymethylimidazole was used.

Example 5

5 parts by mass of a polyphenylmethane-maleimide compound (BMI-2300, manufactured by Daiwa Kasei Co., Ltd.) and 45 parts by mass of a maleimide compound having a structure of the formula (I) (MIR-3000, Japan) A copper-clad laminate was obtained in the same manner as in Example 2 except that 50 parts by mass of MIR-3000 was used instead of the above.

Example 6

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

Example 7

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

Example 8

20 parts by mass of a phenol biphenyl aralkyl type epoxy resin (NC-3000-H, manufactured by Nippon Kayaku Co., Ltd.), and 10 parts by mass of a tetrafunctional 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 instead.

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 phenol resin (SN485, manufactured by Nippon Steel Chemical Co., Ltd.) was used instead of MEHC-7851-H.

Example 10

In the same manner as in Example 2 except that 20 parts by mass of a novolac type cyanate resin (manufactured by PRIMASET PT-30, manufactured by LONZA.J APAN INC.) was used instead of MEHC-7851-H and 0.02 parts by mass of zinc octoate was added thereto. The operation yields a copper clad laminate.

Example 11

15 parts by mass of a phenol biphenyl aralkyl phenol resin (MEHC-7851-H, Mingwa Kasei Co., Ltd.), and 5 parts by mass of a styrene-maleic anhydride copolymer (SMA EF-40, manufactured by Sartomer, USA) were used instead. A copper-clad laminate was obtained in the same manner as in Example 1 except that 20 parts by mass of MEHC-7851-H was used.

Example 12

15 parts by mass of phenol biphenyl aralkyl phenol resin (MEHC-7851-H, Mingwa Kasei Co., Ltd.), and 5 parts by mass of dicyclopentadiene type active ester (HPC-8000-65T, Japan DIC Co., Ltd.) were used instead of 20 A copper-clad laminate was obtained in the same manner as in Example 1 except that the mass fraction of MEHC-7851-H was used.

Example 13

15 parts by mass of a phenol biphenyl aralkyl phenol resin (MEHC-7851-H, Mingwa Kasei Co., Ltd.), and 5 parts by mass of a polyphenylene ether resin (manufactured by SA90, Sabic) were used instead of 20 parts by mass of MEHC-7851-H. Otherwise, a copper clad laminate was obtained in the same manner as in Example 1.

Example 14

In the same manner as in Example 1, except that 120 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 operation yields a copper clad laminate.

Example 15

120 parts by mass of boehmite (A0H-60, manufactured by Nabaltec), and 5 parts by mass of a 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), except Otherwise, a copper clad laminate was obtained in the same manner as in Example 1.

Comparative example 1

50 parts by mass of a maleimide compound (MIR-3000, manufactured by Nippon Kayaku Co., Ltd.) having a structure of the formula (I), and 30 parts by mass of a phenol biphenyl aralkyl type epoxy resin (NC-3000-H) 20 parts by mass of phenol biphenyl aralkyl phenol resin (MEHC-7851-H, Mingwa Kasei Co., Ltd.) was dissolved and mixed with methyl ethyl ketone, and 150 parts by mass of spherical fused silica (SC2500) was further mixed. -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 Industrial Co., Ltd.) Made by the club), get varnish. Since the gelation time of the resin varnish is too short, the processability of producing a copper clad laminate is not obtained.

Comparative example 2

In place of 0.25 parts by mass of 2-phenyl-4-methyl-5-hydroxymethylimidazole, 0.25 parts by mass of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Chemicals Co., Ltd.) was used, and Example 4 was operated in the same manner to obtain a copper clad laminate.

Comparative example 3

The operation was carried out in the same manner as in Example 4 except that 0.25 parts by mass of 2-phenylimidazole (2PZ, manufactured by Shikoku Chemicals Co., Ltd.) was used instead of 0.25 parts by mass of 2-phenyl-4-methyl-5-hydroxymethylimidazole. A copper clad laminate was obtained.

Comparative example 4

In the same manner as in Example 4 except that 2-phenyl-4-methylimidazole (2P4MZ, manufactured by Shikoku Chemicals Co., Ltd.) was used instead of 0.25 parts by mass of 2-phenyl-4-methyl-5-hydroxymethylimidazole. The operation was carried out to obtain a copper clad laminate.

Comparative Example 5

Using 0.25 parts by mass of 2,4-diamino-6-[2'-ethyl-4'-methylimidazolinyl-(1)']-ethyl-s-triazine (2E4MZ-A, Shikoku Chemical Industrial Co., 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-5-hydroxymethylimidazole was used.

Comparative Example 6

0.25 parts by mass of 2,4-diamino-6-[2'-undecyl imidazolinyl-(1)']-ethyl-s-triazine (C11Z-A, manufactured by Shikoku Chemicals Co., Ltd.) was used instead. 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-5-hydroxymethylimidazole was used.

Comparative Example 7

50 parts by mass of polyphenylmethane polymaleimide compound (BMI-2300, manufactured by Daiwa Kasei Co., Ltd.), 30 parts by mass of phenol biphenyl aralkyl type epoxy resin (NC-3000-H, Nippon Chemical Co., Ltd.) 20 parts by mass of phenol biphenyl aralkyl phenol resin (MEHC-7851-H, Mingwa Kasei Co., Ltd.) was dissolved and mixed with methyl ethyl ketone, and 150 parts by mass of spherical fused silica (SC2500-SQ, Admatechs) was further mixed. 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, manufactured by Shikoku Chemicals Co., Ltd.), Get varnish. Since the dissolution of 50 parts by mass of the polyphenylmethane-maleimide compound requires a large amount of solvent, the resin varnish solid content is too low, and the processability for producing a copper-clad laminate is not obtained.

Comparative Example 8

20 parts by mass of a polyphenylmethane-maleimide compound (BMI-2300, manufactured by Daiwa Kasei Co., Ltd.) was used instead of 20 parts by mass of a maleimide compound having a structure of the formula (I) (MIR-3000, Japan) A copper-clad laminate was obtained in the same manner as in Example 6 except that the chemical company was manufactured.

Comparative Example 9

20 parts by mass of bis(3-ethyl-5-methyl-4-maleimidobenzene)methane compound (BMI-70, manufactured by KI Kasei Co., Ltd.) was used instead of 20 parts by mass as the formula ( 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.) of the structure was used.

Comparative Example 10

20 parts by mass of 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane compound (BMI-80, manufactured by KI Kasei Co., Ltd.) was used instead of 20 parts by mass. 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.) of the structure of the above formula (I) was used.

Comparative Example 11

Using the prepreg obtained by the same manufacturing method as in Comparative Example 9, one, four, and eight prepregs were laminated, and an electrolytic copper foil having a thickness of 18 μm was pressed on both sides thereof at a pressure. The machine was cured for 2 hours, the curing pressure was 45 kg/cm ² , and the curing temperature was 220 ° C to obtain a copper-clad laminate having a thickness of 0.1, 0.4, and 0.8 mm.

Comparative Example 12

Using the prepreg obtained by the same manufacturing method as in Comparative Example 10, one, four, and eight prepregs were laminated, and an electrolytic copper foil having a thickness of 18 μm was pressed on both sides thereof at a pressure. The machine was cured for 2 hours, the curing pressure was 45 kg/cm ² , and the curing temperature was 220 ° C to obtain a copper-clad laminate having a thickness of 0.1, 0.4, and 0.8 mm.

Copper-clad laminates prepared in the above Examples 1-15 and Comparative Examples 1-12 according to the measurement methods specifically described above with respect to glass transition temperature (°C), peel strength (N/mm), water absorption (%) , moisture absorption heat resistance (pass is passed by /fail), high temperature (200 ° C) flexural modulus (GPa), plane direction thermal expansion coefficient (CTE: ppm / ° C) and flame retardancy test, the specific results show In Table 1 below.

Table 1

In Comparative Example 1, when the imidazole compound having the same amount and structure was inconsistent as in Example 1, the gelation time was too short to cause no processability; in Comparative Example 7, the maleimide having the same amount and inconsistent structure as in Example 1 was added. In the case of a compound, since the solid content of the varnish is too low, the processability is not obtained, and when the solid content is appropriate, there is a problem that the maleimide compound cannot be completely dissolved, and the processability is not obtained.

Comparative Example 2-6 differs from Examples 1-4 in that the imidazole compound is different, Example 1-4 employs the imidazole compound of the present invention, and Comparative Example 2-6 employs an imidazole compound different from the present invention, and the former has a remarkable advantage. The glass transition temperature (Tg) and water absorption of the latter; Comparative Examples 8-10 differ from Example 6 in that the maleimide compound is different when the maleimide compound of the formula I is not used (comparison In Examples 8-10), the flame retardancy and moisture absorption heat resistance were poor, and the water absorption rate was remarkably high.

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

The above is only some embodiments of the present invention, and various other changes and modifications may be made in accordance with the technical solutions and technical concept of the present invention, and all such changes and modifications should be made by those skilled in the art. It is within the scope of the claims of the present invention.

The present invention is described by the above-described embodiments, but the present invention is not limited to the above detailed methods, and it is not intended that the present invention must be implemented by the above detailed methods. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Claims

A maleimide resin composition, characterized in that the maleimide resin composition comprises:

a maleimide compound (A) having the structure of formula (I);

An imidazole compound (B) having the structure of the formula (II);

Epoxy resin (C); and

Thermosetting resin (D),

In formula (I), R is
a group, 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 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 carbon atoms. Integer

In the formula (II), Ar is a phenyl group, a naphthyl group, a biphenyl group or a hydroxy group 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; Aryl groups of -18 or their hydroxy substitutions, provided that at least one of R 4 and R 5 is phenyl, naphthyl, biphenyl or a hydroxy substituent thereof, or at least one carbon atom having a hydroxy substituent An alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 18 carbon atoms having a hydroxy substituent.
The maleimide resin composition according to claim 1, wherein in the maleimide compound (A) having the structure of the formula (I), n is an integer of from 1 to 15, preferably n. 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 biphenylylene group, and further preferably R1 is a biphenylylene group;

Preferably, R 2 and R 3 are a hydrogen atom.
The maleimide resin composition according to claim 1 or 2, wherein the epoxy resin (C) is selected from the group consisting of a novolac type epoxy resin, a cresol novolac type epoxy resin, and a naphthol. At least one of a phenolic epoxy resin, a fluorene epoxy resin, a phenolphthalein epoxy resin, an aralkyl phenolic epoxy resin, and an epoxy resin having an arylene ether structure in its molecule.
The maleimide resin composition according to any one of claims 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. Copolymer resin, active ester resin, benzoxazine resin, polyphenylene ether resin, silicone resin, amine compound, dicyclopentadiene resin and copolymerization with epoxy resin and/or maleimide resin At least one of the compounds.
The maleimide resin composition according to any one of claims 1 to 4, wherein the maleimide resin composition further comprises 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.
The maleimide resin composition according to any one of claims 1 to 5, wherein the maleimide resin (A), the epoxy resin (C) and the thermosetting resin (D) are used. 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 the thermosetting resin (D) is from 1 to 70 parts by mass; preferably, when the inorganic filler (E) is contained, 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.
A prepreg comprising a substrate and a maleimide resin composition according to any one of claims 1 to 6 which is adhered to the substrate after impregnation and drying.
A laminate characterized in that the laminate comprises at least one prepreg according to claim 7.
The laminate according to claim 8, wherein said laminate is a metal foil laminate, said metal foil laminate comprising at least one prepreg according to claim 7 and overlying prepreg A metal foil on one or both sides of the material.
A printed wiring board characterized in that the printed wiring board comprises at least one prepreg according to claim 7.