JP4676739B2 - Resin composition and prepreg and laminate using the same - Google Patents

Description

  The present invention relates to a resin composition used in the field of electronic materials such as electronic / electrical components, printed wiring boards, semiconductor substrates, and IC encapsulants, and uses thereof. More specifically, the present invention relates to a light and thin material particularly for printed wiring boards and semiconductor substrates. The present invention relates to a resin composition that is suitable for shortening and has a high elastic modulus and strength and good workability, and a prepreg and a laminate using the resin composition.

  As electronic devices have become lighter and thinner in recent years, the thickness of thin packages that require space saving, such as memory cards and circuit boards for mobile phones, and the thickness of laminates used for thin substrates are 0.5 mm or less, preferably 0 .2 mm or less is required. The thinner the thickness, the more likely it is to warp and bend easily in the process of circuit formation or in the process of conveyance. This is a problem caused by the thinness of the substrate and the laminate, resulting in a lack of rigidity of the substrate, in this case, the rigidity of the substrate at room temperature.

  On the other hand, when a thin substrate is used, the coefficient of thermal expansion is not limited even when exposed to high temperatures in semiconductor mounting processes using ACP, ACF, etc. that require high temperatures, or secondary mounting processes using solder reflow, etc. As a result of the stress caused by the difference between the two, the substrate is warped or bent, causing problems such as mounting defects. This is due to the fact that the laminate is not sufficiently rigid at high temperatures against stresses caused by high temperatures.

  From the above, in order to solve problems such as warpage during transport in the process and mounting defects during mounting, a substrate material that retains high rigidity at both room temperature and high temperature is required. .

  As a general technique for increasing the rigidity, there are general techniques such as a method in which a glass cloth to be used is made of high hardness glass (S glass, H glass, etc.), a method in which the number of glass cloths to be used is increased, and the like. (Refer to patent document 1 etc.). However, glass with high hardness is more expensive than ordinary glass cloth (E glass) and has disadvantages such as poor workability such as drilling. On the other hand, when the number of stacked sheets is increased, there is a problem that the number of used prepregs per stacked sheet increases and the cost increases.

  On the other hand, a technique of increasing the rigidity by blending an inorganic filler in the resin composition has also been studied. In particular, a technique of increasing the rigidity of a resin composition by containing a high volume fraction of an inorganic filler is known (see Patent Document 2). However, as the volume fraction of the inorganic filler is increased, problems such as peeling at the interface between the resin and the filler during processing, and the adhesive strength between the prepregs being lowered in the laminated plate are likely to occur.

In addition, when an inorganic filler having high rigidity such as silica is used, there is a problem that the wear of the drill is remarkable at the time of drilling, and the hole position system and the hole wall roughness are deteriorated. Therefore, when using a highly rigid inorganic filler such as silica, there are measures such as blending a specific particle size (see Patent Document 3) or using a filler having low hardness (see Patent Document 4). It was taken, but the effect was not enough.
JP 2001-329080 A JP-A-8-216335 Japanese Patent Laid-Open No. 2003-020407 JP 2000-117733 A

  The problem of the present invention is that the resin composition has a high rigidity, and has a sufficient rigidity even when a laminate of 0.2 mm or less is formed using the resin composition, and has a workability such as drillability. It is to provide an excellent laminate.

  As a result of intensive studies to solve the above problems, the present applicant is obtained by firing talc into a resin composition containing a compound (A) having a maleimide group as a resin composition used for a laminate ( When a specific amount of B) is contained, a highly heat-resistant resin matrix is filled with highly rigid inorganic compound particles so as to overlap each other. The present invention was completed by finding out that the product can be obtained.

That is, the present invention relates to the following.
(1) a compound having a maleimide group (A), made by firing talc (B), an epoxy resin, and contains a phenolic resin having at least one naphthalene ring, a compound containing the maleimide group (A) However, it is a compound containing two or more maleimide groups, which is obtained by baking the talc (B), containing 30 parts by mass or more and 250 parts by mass or less with respect to 100 parts by mass in total of the resin components. A resin composition characterized by the above.
(2) The resin composition according to (1), wherein the compound (A) containing the maleimide group is contained in an amount of 5% by mass to 70% by mass with respect to the total mass of the resin components.
( 3 ) The resin composition according to (1) or (2) , wherein the epoxy resin is contained in an amount of 10% by mass to 50% by mass with respect to the total mass of the resin components.
(4) a phenolic resin having at least one naphthalene ring, relative to the total mass of the resin component, those containing more than 10 wt% 50 wt% or less (1) to (3) in any one The resin composition as described.
( 5 ) A prepreg obtained by impregnating a base material with the resin composition according to any one of (1) to ( 4 ).
( 6 ) A laminate obtained by heat-curing one or a plurality of prepregs described in ( 5 ).
( 7 ) A laminate comprising a resin obtained from the resin composition according to any one of (1) to ( 4 ) as an insulating layer.

  Since the resin composition of the present invention has high rigidity, even when it becomes a thin laminate of 0.2 mm or less, a sufficiently high elastic modulus can be obtained at both normal temperature and high temperature. Moreover, although the elastic modulus of the resin composition is high, it is excellent in workability such as drilling.

Hereinafter, the present invention will be described in detail.
In the resin composition of the present invention, a resin composition containing a maleimide group-containing compound (A) and baked talc (B) is 30 parts by mass with respect to 100 parts by mass in total of the resin composition. More than 250 parts is contained. First, each component which comprises the resin composition of this invention is demonstrated.

Compound having maleimide group (A)
The compound having a maleimide group used in the present invention is not particularly limited as long as it has a maleimide group, but is preferably a compound having two or more maleimide groups as represented by the following general formula (1). .

(In the formula, R ₁ represents an m-valent organic group. In the formula, m is preferably 2 to 10. The organic groups represented by R ₁ include the following general formulas (2-1) to (2-3). Preferred examples include those selected from the group consisting of:

(In the formula, Xs may be the same or different from each other, and are —CH ₂ —, —C (CH ₃ ) ₂ —, —C (C ₂ H ₅ ) ₂ —, —CO—, —O—, — ( Single bond), —S— or —SO ₂ —, Y may be the same or different from each other, and represents —CH ₃ , —CH ₂ CH ₃ , or a hydrogen atom.

  Specific examples of the compound containing at least two or more maleimide groups used in the present invention include, for example, N, N ′-(1,3-phenylene) bismaleimide, N, N ′-[1,3- (2 -Methylphenylene)] bismaleimide, N, N '-(1,4-phenylene) bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, bis (4-maleimide) Phenyl) ether, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, 1,4-bis (maleimidomethyl) benzene, 1,3-bis (3- Maleimidophenoxy) benzene, bis [4- (4-maleimidophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimi Phenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (4-maleimidophenoxy) phenyl] ethane and the like.

  Moreover, as a compound containing the at least 2 or more maleimide group used by this invention, following General formula (3)

(Wherein n is an average value of 0 to 10) and a compound containing a maleimide group represented by the following general formula (4)

(Wherein, n is an average value of 0 to 10), and a compound containing a maleimide group. These compounds (A) containing at least two or more maleimide groups can be used singly or in combination of two or more.

Baked talc (B)
As the baked talc used in the present invention (B), talc existing as a natural mineral can be baked and used, or an industrially produced talc can be used. Since talc _{(3MgO · 4SiO 2 · H 2} O) is having a crystal water and releases the crystal water by firing at a high temperature of more than about 700 ° C.. For example, it is possible to release crystal water by firing at a temperature of 1000 ° C. to 1500 ° C. for about 5 to 20 hours. As the talc used in the present invention, for example, a so-called calcined talc is used which releases crystal water by firing as described above. When what is obtained as a mineral is baked, it may contain oxides such as aluminum oxide, calcium oxide, potassium oxide and iron oxide as trace components, but can be used without any particular problem.

  It is important that the content of the baked talc (B) is 30 to 250 parts by mass with respect to a total of 100 parts by mass of the resin component (component (A) + other resin component). is there. Preferably they are 50 to 150 mass parts. If the addition amount is 30 parts by mass or more, the effect of addition can be expected. If the addition amount is 250 parts by mass or less, the viscosity of the resin varnish is good and the impregnation property is good. Although there is a part depending on the type of compound to be added, if the addition amount is in the above range, the elastic modulus of the cured resin is improved, and the bending elastic modulus when it becomes a laminated plate tends to be a preferable value of 20 GPa or more. .

  The baked talc has a higher crystal hardness than the unfired talc. Therefore, when the case where each was contained in the resin composition containing the compound containing a maleimide group was compared, it discovered that the direction which contained what baked the talc had an effect which raises an elasticity modulus notably.

  In addition, the baked talc (B) is an inorganic compound having a layered structure, so that the particles are plate-like, and the aspect ratio (ratio between the vertical length and the horizontal length of the particles) is high. When a resin composition filled with such plate-like particles is used as a prepreg, in the impregnation coating process, it is easy to fill the resin so that they overlap each other. It is thought that it contributes to improvement in elastic modulus. As the particle size of these inorganic compounds, the average particle size D50 is preferably in the range of 0.1 μm or more and less than 10.0 μm. A thickness of 0.1 μm or more is preferable because secondary aggregation or the like does not occur during handling, and it is easy to disperse uniformly. Further, it is preferable that D50 is 10.0 μm or less because sedimentation or the like hardly occurs when the resin varnish is formed, and stability is good.

  It is preferable that the talc used in the present invention (B) is subjected to a surface treatment with a coupling agent. It does not specifically limit as a kind of coupling agent required for surface treatment, A silane coupling agent, a titanate coupling agent, etc. are mentioned as an example. A silane coupling agent is particularly preferable. Examples of silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, N-phenyl-γ-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc., and one or more of these are used. The These silane coupling agents are preferably fixed to the surface of calcinated talc (B) by adsorption or reaction.

Epoxy resin The resin composition of the present invention preferably further contains an epoxy resin. The epoxy resin that can be used is not particularly limited, but is preferably an epoxy resin having at least two glycidyl groups in the molecule. Examples of these include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, etc. The dicyclopentadiene type epoxy resin etc. which are shown by (5) are also mentioned.

(In the formula, G is a glycidyl group, and l is an average value of 0 to 6)
Furthermore, an epoxy resin obtained by reacting epichlorohydrin with a compound containing two or more phenolic hydroxyl groups, such as dihydroxynaphthalene, phenol aralkyl resin, naphthol aralkyl resin, phenol aralkyl resin containing a naphthalene ring, or novolak resin containing a naphthalene skeleton, or The epoxy resin containing the naphthalene ring shown by following General formula (6) is also mentioned.

(In the formula, G is a glycidyl group, j is an average value of 0 to 10)
Among these epoxy resins, an epoxy resin containing a naphthalene ring is preferable, and an epoxy resin containing a naphthalene ring represented by the following general formulas (7) and (8) is more preferable.

(In the formula, G represents a glycidyl group, q ₁ and q ₂ represent an integer of 1 or more, and q ₁ + q ₂ ≦ 8)

(In the formula, G represents a glycidyl group, p represents 1 or 2, and n represents an integer of 1 to 10)
In addition, these epoxy resins can be used individually or in combination of 2 or more types.

Phenol resin The resin composition of the present invention preferably further contains a phenol resin. The phenol resin that can be used is a compound having at least one phenolic hydroxyl group. Although it does not receive a restriction | limiting especially if this condition is satisfy | filled, it is preferable to have at least 1 naphthalene ring. Specific examples include the following.

  Examples thereof include hydroxynaphthalenes such as naphthol, dihydroxynaphthalene, trihydroxynaphthalene, and tetrahydroxynaphthalene. Moreover, the compound etc. which are obtained by making hydroxy naphthalenes and the mixture of these hydroxy naphthalenes and phenols react with aldehydes are mentioned. Specific examples of these compounds include compounds represented by the general formula (9). Examples of phenols include phenol, cresol, resorcinol, and examples of aldehydes include formaldehyde, acetaldehyde, benzaldehyde, and the like.

(Where j is an average value of 0 to 10)
In addition, although these compounds can also be obtained by the said method, it is also possible to use Nippon Kayaku Co., Ltd. product name: Kayahard NHN etc. as a commercial item which can be used.

  Alternatively, hydroxy naphthalenes, and a compound obtained by reacting a mixture of these hydroxy naphthalenes and phenols with an aralkyl alcohol derivative or an aralkyl halide derivative can be used. Specific examples of these compounds include compounds represented by general formula (10). Examples of phenols include phenol, cresol, and resorcinol. Examples of aralkyl alcohol derivatives include p-xylylene glycol and p-xylylene glycol dimethyl ether. Examples of aralkyl halide derivatives include p-xylylene dichloride.

(Wherein p represents 1 or 2, n represents an integer of 1 to 10)
In addition, although these compounds can also be obtained by the said method, it is also possible to use Nippon Steel Chemical Co., Ltd. product name: SN180 etc. as a commercial item which can be used. These compounds having a phenolic hydroxyl group can be used alone or in combination of two or more.

Resin Composition In the resin composition of the present invention, the content of the compound (A) containing a maleimide group is 5% by mass or more and 70% by mass with respect to the total mass of the resin component ((A) + other resin component). % Or less, more preferably 30% by mass or more and 60% by mass or less. When the content of (A) is 5% by mass or more, preferably 30% by mass or more, the composition has high rigidity and a high elastic modulus at high temperatures can be expected. On the other hand, the content of 70% by mass or less is preferable because the resin composition has a low hygroscopic property and has sufficient heat resistance under a hygroscopic condition such as a solder heat test.

  Furthermore, when the epoxy resin is contained in the resin composition, the content of the epoxy resin is preferably 10% by mass or more and 50% by mass or less with respect to the total mass of the resin components. When the content is 10% by mass or more, the resin is less brittle, and when the content is 50% by mass or less, the thermal curing speed of the resin is high, and the time required to complete the curing is short. .

  Moreover, it is preferable to contain 10 mass% or more and 50 mass% or less of content of the phenol resin in the case of containing a phenol resin with respect to the sum total of the mass of a resin component. When the content is 10% by mass or more, the resin is less brittle, and when the content is 50% by mass or less, the thermal curing speed of the resin is high, and the time required to complete the curing is short. .

Other resin components The resin composition of the present invention can contain other resin components as needed in addition to the above-mentioned various components. Preferable examples include thermoplastic resins, reactive diluents, and the like, and these may be added as long as the object of the present invention is not impaired.

  The thermoplastic resin is not particularly limited, but preferred examples include polyethersulfone, polysulfone, polyphenylene sulfide, polyetheretherketone, polyimide, polyetherimide, polyamideimide, aromatic polyamide, polyparaban having a molecular weight of 5000 to 100,000. Examples include acids, polyphenylene ethers, phenoxy resins, and liquid crystal polymers such as aromatic polyesters. Further, those obtained by grafting a carboxyl group, a hydroxyl group, an alkene group or the like to the terminal or side chain can be used more suitably. When the molecular weight of these thermoplastic resins is 5000 or more, the effect of imparting flexibility by the polymer can be obtained, and when the molecular weight is 100,000 or less, the viscosity does not become too high and the moldability is sufficient. preferable.

  As for content of a thermoplastic resin, it is desirable to use in the range of 0.1-30 mass% with respect to the resin component of the said resin composition. The addition effect is obtained when the content is 0.1% by mass or more, and the heat resistance of the resin composition can be maintained when the content is 30% by mass or less.

  As the reactive diluent, reactive diluents commonly used for epoxy resins such as glycidol, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, diallyl phthalate, o, o'- Examples include compounds having an allyl group such as diallyl bisphenol A and bisphenol A diallyl ether (these are reactive diluents generally used for thermosetting imide resins). The content of these reactive diluents is desirably used in the range of 0.1 to 10% by mass with respect to the resin component. If it is 0.1% by mass or more, the effect as a reactive diluent is sufficient, and if it is 10% by mass or less, the viscosity of the resin varnish made of the resin composition does not decrease too much and the workability is good. is there.

Flame retardant The resin composition of the present invention may further contain a flame retardant. Examples of the flame retardant that can be used in the resin composition of the present invention include known flame retardants such as a bromine-containing flame retardant, a phosphorus-containing flame retardant, and a metal hydroxide.

  Examples of bromine-containing flame retardants are not particularly limited, but preferred examples include tetrabromobisphenol A, epoxy resins obtained by reacting tetrabromobisphenol A and epichlorohydrin, oligomers thereof, and polymers thereof. Also, bromine-containing maleimide compounds such as bromine-substituted phenylmaleimide can be used. These brominated flame retardants can be used alone or in combination of two or more.

  The addition amount of the bromine-containing flame retardant is preferably in the range of 3 to 7% by mass with respect to the total mass of the resin components in terms of elemental bromine. This range is preferable because flame retardancy can be obtained and the heat resistance of the resin composition can be maintained.

  Examples of phosphorus-containing flame retardants include aromatic condensed phosphoric acid condensed with phosphoric esters such as triphenyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, tris (isopropylphenyl) phosphate, etc. Examples include esters. These phosphorus-containing flame retardants can be used alone or in combination of two or more.

  As addition amount of a phosphorus-containing flame retardant, the range of 0.3-3 mass% is preferable with respect to the total mass of a resin component in conversion to a phosphorus element. This range is preferable because flame retardancy can be obtained and the moisture resistance of the resin composition can be maintained.

As the metal hydroxide, a metal compound having (OH) _n such as aluminum hydroxide, magnesium hydroxide, and zinc hydroxystannate is preferable. (OH) ₃ ), magnesium hydroxide (Mg (OH) ₂ ), and zinc hydroxystannate (ZnSn (OH) ₆ ) are more preferable, and aluminum hydroxide is still more preferable. These metal hydroxides preferably have a low content of Na ₂ O contained as impurities. The content of Na ₂ O is preferably less than 0.3%, more preferably 0.2% or less, and particularly preferably 0.1% or less. METHOD If Na ₂ O amount is large for cleaning which is contained as an impurity in the metal hydroxide, by a method such as is described, for example, in JP-A-8-325011 discloses a Na ₂ O content contained 0 It is preferable to use after reducing to less than 3%. When the Na ₂ O content of the metal hydroxide is within the above range, the laminate obtained from the heat resistant resin composition containing the metal hydroxide is excellent in solder heat resistance. Further, when the laminate is used as a circuit board, it is difficult to cause reliability deterioration due to ion migration. When the metal hydroxide is used in the resin composition of the present invention, the particle size of the metal hydroxide is not particularly limited, but those having an average particle size of about 0.1 to 10 μm are usually used. These metal hydroxides can be used alone or in combination of two or more.

  Moreover, it is preferable to use a coupling agent for said metal hydroxide. As the coupling agent, coupling agents such as silane, titanate, aluminate and zircoaluminate can be used. Among these, a silane coupling agent is preferable, and a silane coupling agent having a reactive functional group is even more preferable.

  Examples of silane coupling agents are vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxy. Silane, N-phenyl-γ-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc., and one or more of these are used. The These silane coupling agents are preferably fixed in advance to the surface of the metal hydroxide by adsorption or reaction. When the coupling agent is used, the adhesion between the metal hydroxide and the resin is improved, and the mechanical strength and heat resistance of the laminate obtained from the resin composition can be expected.

  The metal hydroxide is preferably 5 to 100 parts by mass, more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the total resin components. When the content of the metal hydroxide is within the above range, the flame retardancy effect is obtained, the viscosity when made into a varnish is appropriate, the impregnation property to the substrate is good, and the workability is excellent. In addition, when the content of the metal hydroxide is 100 parts by mass or less (when the content is 50% by mass or less of the resin composition), the water absorption of the resin composition does not increase, and the solder heat resistance after moisture absorption is high. It is preferable because it is less likely to adversely affect the properties.

Curing Accelerator The resin composition of the present invention preferably contains a curing accelerator. Examples of curing accelerators include imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole tetraphenylborate; triethanolamine, triethylenediamine, Amines such as N-methylmorpholine; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triethylammonium tetraphenylborate; 1,8-diaza-bicyclo (5,4,0) undecene-7 and derivatives thereof Can be mentioned. These curing accelerators can be used alone or in combination of two or more.

  The content of these curing accelerators is preferably blended so as to obtain the desired gelation time of the varnish or prepreg described later, but generally 0% relative to 100 parts by mass of the total amount of resin components. It is used in the range of 0.005 to 10 parts by mass.

Additives Additives can also be added to the resin composition of the present invention depending on the application. Preferable examples of the additive include an antifoaming agent, a leveling agent, an additive generally used as a surface tension adjusting agent, and the like. Specific examples include fluorine-based, silicone-based, acrylic-based antifoaming agents, and leveling agents. The content of the additive is generally preferably used in the range of 0.0005 to 10 parts by mass with respect to 100 parts by mass of the total amount of the resin components.

Preparation method of resin composition The resin composition of the present invention comprises, for example, a compound (A) containing a maleimide group, an epoxy resin and / or a phenol resin, and / or other resin components at 80 to 200 ° C, 0 1. It can be heated and mixed for 1 to 10 hours to make a uniform mixture. In the case of calcination of talc (B), the above mixture can be pulverized at room temperature and mixed in a powder state, or after the resin component is made into a resin varnish by the method described below, Compounds can also be mixed.

Resin varnish The resin varnish of the present invention is obtained by dissolving a compound (A) containing a maleimide group and calcinated talc (B), an epoxy resin, and / or a phenol resin, and / or other resin components in a solvent. It has been done.

  Solvents used in the resin varnish include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, dioxane, acetone, N-methyl-2-pyrrolidone , Dimethyl sulfoxide, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, 2-heptanone and the like. As the solvent, those having a relatively low boiling point are preferable, and methyl ethyl ketone, acetone, dioxane or a mixture containing these as a main component is preferably used.

  The resin varnish of the present invention is obtained by baking the compound (A) containing the maleimide group and talc (B), an epoxy resin, and / or a phenol resin, and / or within the range not impairing the object of the present invention. Or other resin components may be contained. The content of the compound (A) containing the maleimide group in the resin varnish and the baked talc (B), the epoxy resin, and / or the phenol resin, and / or other resin components is the same as that of the resin composition. It is the same.

  The resin varnish of the present invention preferably contains the curing accelerator as described above, and the content is the same as described above. Further, the resin varnish of the present invention can contain “other resin components” which the resin composition may contain. In the resin varnish, the total mass of the resin components is usually 50 to 80% by mass, preferably 55 to 75% by mass.

  The resin varnish can be obtained by dissolving the resin composition in an organic solvent, or a compound (A) containing a maleimide group in an organic solvent, an epoxy resin, and / or a phenol resin, and / or other It can adjust by heating and mixing with a resin component to make a uniform solution. Although the temperature at the time of heating and mixing depends on the boiling point of the organic solvent, it is usually 50 to 200 ° C., and the heating and mixing time is usually 0.1 to 20 hours.

Prepreg In the prepreg of the present invention, a base material is impregnated with the resin composition. The prepreg of the present invention can be produced by applying or impregnating the resin varnish to a substrate and then drying to remove the solvent. As a base material, all the well-known base materials used for conventional prepregs, such as a glass nonwoven fabric, a glass cloth, a carbon fiber cloth, an organic fiber cloth, paper, can be used. After applying or impregnating the resin varnish to the base material, a prepreg is produced through a drying step, and the coating method, impregnation method and drying method are not particularly limited, and conventionally known methods are used. The drying conditions are appropriately determined depending on the boiling point of the solvent to be used, but it is desirable that the amount of the residual solvent in the prepreg is 1% by mass or less. As a specific example, a residence time of about 5 minutes to 10 minutes is preferable in the range of 140 ° C. to 220 ° C., but in the manufacturing process in which the prepreg is continuously dried, the optimum temperature range is the conveyance. This is not the case because it changes depending on the speed.

Laminate The laminate of the present invention is characterized in that one or a plurality of the prepregs are laminated and heat-cured by hot pressing. The heating and pressing conditions for producing the laminated plate are not particularly limited, but the heating temperature is preferably 100 to 300 ° C, more preferably 150 to 250 ° C, and the pressure is preferably 1.0 to 10 MPa. The heating and pressing time is preferably about 10 to 300 minutes.

  Moreover, the laminated board of this invention may be integrated by laminating | stacking metal foil or a metal plate on both surfaces. In that case, a metal foil or a metal plate is laminated on one or both sides of one prepreg and heat-pressed, or a metal foil or a metal plate is laminated on both surfaces which are the outermost layers of a plurality of laminated prepregs. By doing so, the prepreg can be manufactured by heat-curing and integrating. As the metal foil or metal plate, copper, aluminum, iron, stainless steel or the like can be used. The conditions for heat-curing are the same conditions as for the laminate.

  Furthermore, the laminated board of the present invention is obtained by alternately laminating prepregs on the both sides of the above laminated board, further laminating a metal foil or metal plate on the outermost layer, and thermocompression bonding. A multilayer laminate having the resin composition as an insulating layer is also included. The multilayer laminate of the present invention can be produced using various methods used in the production process of a general laminate for a multilayer printed wiring board, and is not particularly limited by the construction method.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

Examples 1-3 and Comparative Examples 1-2
Among the compositions shown in Table 1, a compound of maleimide-containing compound (A), epoxy resin, phenol resin and other resin was mixed in a flask with a mixed solvent of methyl ethyl ketone: N-methyl-2-pyrrolidone (mixing ratio is methyl ethyl ketone). : N-methyl-2-pyrrolidone = 4: 1) and dissolved at 80 ° C. for 6 hours to obtain a resin varnish. The resin varnish obtained in this manner is obtained by baking talc (B) or other inorganic compound, and uniformly stirring the mixture on a release film with a thickness of about 20 μm, and 100 ° C. After drying for 30 minutes, the film is peeled off and pulverized to obtain a resin composition powder. The resin composition powder was placed in a 3 cm × 6 cm mold and molded at 180 ° C. to 230 ° C. for 120 minutes under a pressure of 2 MPa. Thereafter, these molded products were cut into 2.5 cm × 5 cm with a diamond cutter to obtain a resin plate having a thickness of about 2.0 mm. The bending strength and elastic modulus of these resin plates were measured according to ASTM D790-00. In addition, the unit of each component in a table | surface is a mass part.

Examples 4-7 and Comparative Examples 3-4
Among the compositions shown in Table 2, a compound of maleimide-containing compound (A), epoxy resin, phenol resin and other resin was mixed in a flask with a mixed solvent of methyl ethyl ketone: N-methyl-2-pyrrolidone (mixing ratio is methyl ethyl ketone). : N-methyl-2-pyrrolidone = 4: 1) and dissolved at 80 ° C. for 6 hours to obtain a resin varnish. A resin varnish obtained by firing talc (B) or other inorganic compound, a curing accelerator, a flame retardant, and an additive were added and stirred uniformly to obtain a uniform resin varnish. These varnishes were impregnated into a glass cloth of 108 g / m ² (thickness: about 100 μm) and dried at 150 ° C. for 5 minutes to obtain a prepreg of about 200 g / m ² (thickness: about 100 μm). Sixteen prepregs are stacked, and 18 μm copper foil is disposed on the upper and lower outermost layers, and molded under a pressure of 2 MPa at 180 to 230 ° C. for 120 minutes, and 1.6 to 1.7 mm. A thick copper-clad laminate was obtained. The results of bending tests of the laminates thus obtained are also shown in the table. The test method is shown below. Moreover, about the evaluation of the elasticity modulus of the laminated board of 0.2 mm or less, using the copper clad laminated board of thickness 0.2-0.3mm created similarly to the above except having piled up two prepregs. went. Furthermore, for evaluation of workability, a 0.4 to 0.5 mm copper-clad laminate prepared by superimposing four prepregs in the same manner was tested with a drilling machine having a diameter of 0.15 mm under the condition (3) below. Processed and evaluated by the breakage rate of the drill.

(1) Bending strength and elastic modulus: Measured according to JIS C6481 5.8.
(2) Thin plate elastic modulus: Measured according to JIS C6481 5.17.2, and the storage elastic modulus at 50 ° C. and 200 ° C. was defined as the elastic modulus at normal temperature and high temperature, respectively.
(3) Workability: Using a drill made by Union Tool (NEV0.15 × 2.5E962S), drilling holes at 3 stacks, rotating at 160Krpm, feeding speed 1.2m / min, and using 10 drills The number of breakage of the drill at that time was taken as the breakage rate.

In the examples and comparative examples, the following raw materials were used.
(A) a compound containing a maleimide group;
BMI-S (trade name, nitrogen atom content: about 8%, molecular weight: 358, manufactured by Mitsui Chemicals, Inc.)
BMI-MP (trade name, nitrogen atom content: about 10%, molecular weight: 268, manufactured by Mitsui Chemicals, Inc.)
(B) those obtained by firing talc and other inorganic compounds;
Firing talc; BST (trade name, average particle size: 5 μm, manufactured by Nippon Talc Co., Ltd.)
Baked talc; SG95 fired product (average particle size: 3 μm, manufactured by Nippon Talc Co., Ltd.)
Firing talc: SG2000 calcined product (average particle size: 2 μm, manufactured by Nippon Talc Co., Ltd.)
Talc: SG2000 (trade name, average particle size: 2 μm, manufactured by Nippon Talc Co., Ltd.)
Silica; SO-C5 (trade name, average particle size: 1.7 μm, manufactured by Tatsumori Co., Ltd.)
Epoxy resin;
Bisphenol A type epoxy resin Epicoat 828EL (epoxy equivalent 190, manufactured by Japan Epoxy Resins Co., Ltd.)
Dicyclopentadiene type epoxy resin Epicron HP7200 (epoxy equivalent 250, manufactured by Dainippon Ink & Chemicals, Inc.)
Naphthalene type epoxy resin, Epicron HP4032 (trade name, epoxy equivalent 150, manufactured by Dainippon Ink & Chemicals, Inc.)
Naphthol aralkyl epoxy resin, ESN175 (trade name, epoxy equivalent 270, manufactured by Nippon Steel Chemical Co., Ltd.)
Phenolic resin;
Naphthol aralkyl resin, SN180 (trade name, OH equivalent 190, manufactured by Nippon Steel Chemical Co., Ltd.)
Naphthol aralkyl resin, SN485 (trade name, OH equivalent 215, manufactured by Nippon Steel Chemical Co., Ltd.)

Other resin compositions:
Reactive diluent: Allyl glycidyl ether (Epiol A (trade name), manufactured by NOF Corporation)
Flame retardants:
Brominated bisphenol A epoxy resin (Epicoat 5050 (trade name), manufactured by Japan Epoxy Resins Co., Ltd.)
Curing accelerator; 2-ethyl-4-methylimidazole (2E4MZ (trade name), manufactured by Shikoku Kasei Kogyo Co., Ltd.)
Additive: FTX218 (trade name, manufactured by Neos Co., Ltd.)

  Compared to the Examples, Comparative Example 1 has low bending strength and elastic modulus because no inorganic compound is added. Since Comparative Example 2 is not a fired product, it can be seen that the flexural modulus is low.

  Compared to the examples, Comparative Example 3 has a low elastic modulus and strength because the inorganic compound is not a fired product, and Comparative Example 4 has a low drilling workability due to the addition of silica, but the drillability is poor. It breaks.

  Even when a wiring board is formed in a thin form of 0.2 mm or less, it has a high elastic modulus at both room temperature and high temperature, so that it is difficult to cause a problem of yield deterioration due to substrate warpage or the like, and it can be used for electronic substrate materials that are light and thin. it can.

Claims (7)

Containing a maleimide group-containing compound (A), a product obtained by baking talc (B), an epoxy resin, and a phenol resin having at least one naphthalene ring;
The compound (A) containing the maleimide group is a compound containing two or more maleimide groups, and is obtained by firing the talc (B) with respect to 100 parts by mass of the resin components in total. A resin composition characterized by containing not less than 250 parts by mass. The resin composition according to claim 1, wherein the compound (A) containing the maleimide group is contained in an amount of 5% by mass to 70% by mass with respect to the total mass of the resin components. The resin composition according to claim 1 or 2 , wherein the epoxy resin is contained in an amount of 10% by mass to 50% by mass with respect to the total mass of the resin components. The resin composition according to any one of claims 1 to 3, wherein the phenol resin having at least one naphthalene ring is contained in an amount of 10% by mass to 50% by mass with respect to the total mass of the resin components. . A prepreg obtained by impregnating a base material with the resin composition according to any one of claims 1 to 4 . A laminate comprising one or a plurality of laminated prepregs according to claim 5 which is heat-cured. A laminate comprising a resin obtained from the resin composition according to any one of claims 1 to 4 as an insulating layer.