JP2017141314A - Prepreg - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a prepreg capable of achieving low Dk and low Df.SOLUTION: There is provided a prepreg which contains a resin composition having a dielectric constant (Dk) of 2.5 or more and 2.7 or less and a dielectric loss tangent (Df) of 0.005 or more and 0.007 or less, a glass fiber base material, and an inorganic filler, where the glass fiber base material is 5 vol.% or more and 30 vol.% or less, the resin composition is 45 vol.% or more and 90 vol.% or less, and the inorganic filler is 3 vol.% or more and 35 vol.% or less, based on specific gravity; and the inorganic filler may contain silica.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a prepreg. In particular, the present invention relates to a prepreg capable of realizing low Dk and low Df.

  In recent years, the speed and capacity of data communication used in information communication has been rapidly increased. Therefore, in the above electronic devices, printed wiring boards that satisfy both high frequency characteristics and multilayer wiring are required.

  A printed wiring board used for information communication is required to have a low dielectric constant (low Dk) and a low dielectric loss tangent (low Df) in order to reduce signal propagation delay and transmission loss. In order to realize these requirements, a resin material containing polyphenylene ether is used as an insulating layer between wirings that are multilayered in a printed wiring board. Polyphenylene ether is a compound that has excellent electrical characteristics (low dielectric constant and low dielectric loss tangent) and is expected to be effective in increasing transmission speed and reducing transmission loss. Attempts have been made to apply this prepreg laminate using polyphenylene ether to a printed wiring board in order to improve the performance and the multilayer structure of the printed wiring board.

  In addition, as the performance of printed wiring boards increases and the number of layers increases, the materials for laminated boards used for printed wiring boards are required to be thin and have high rigidity. In order to satisfy these requirements, for example, in Patent Document 1 and Patent Document 2, a prepreg using a glass cloth as a base material is used.

JP 2002-194212 A JP-A-10-273518

  However, in Patent Document 1 and Patent Document 2, in the characteristic values of dielectric constant (Dk) and dielectric loss tangent (Df), low Dk and low Df are limited due to the glass cloth included in the substrate. Is known.

  This invention is made | formed in view of such a subject, and it aims at providing the prepreg which can implement | achieve low Dk and low Df.

  A prepreg according to an embodiment of the present invention includes a resin composition having a dielectric constant (Dk) of 2.5 to 2.7 and a dielectric loss tangent (Df) of 0.005 to 0.007, and glass fiber. A glass fiber substrate based on specific gravity is contained in an amount of 5% by volume to 30% by volume, a resin composition is 45% by volume to 90% by volume, and an inorganic filler is 3% by volume to 35%. % By volume or less.

  Further, the inorganic filler may contain silica.

ここで、式中、Ｘはアリール基を示し、（Ｙ）ｍはポリフェニレンエーテル部分を示し、Ｒ¹〜Ｒ³は独立して水素原子、アルキル基、アルケニル基またはアルキニル基を示す。ｎは１〜６の整数を示し、ｑは１〜４の整数を示す。 Further, the resin composition is a polyphenylene ether resin composition represented by the following formula (I), may include a polyphenylene ether cross-linking type curing material, and may have a number average molecular weight of 1000 to 7000.

Here, in the formula, X represents an aryl group, (Y) m represents a polyphenylene ether moiety, and R ^{1 to} R ³ independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. n shows the integer of 1-6, q shows the integer of 1-4.

  Further, the resin composition has an epoxy compound having a number average molecular weight of 1000 or less and not containing a halogen atom having at least two epoxy groups in one molecule, a polyphenylene ether having a number average molecular weight of 5000 or less, a cyanate ester compound, and an epoxy compound. And a curing catalyst that promotes the reaction between the polyphenylene ether and the cyanate ester compound that is a curing agent, and a halogen-based flame retardant.

  According to the present invention, it is possible to provide a prepreg capable of realizing low Dk and low Df.

It is a table | surface which shows the structure and evaluation result of a prepreg which concern on one Example of this invention. It is a table | surface which shows the structure and evaluation result of a prepreg which concern on one Example of this invention.

<Embodiment 1>
Hereinafter, the prepreg according to the present invention will be described in detail. However, the prepreg of the present invention is not construed as being limited to the description of the following embodiments and examples.

[Configuration of prepreg]
When a prepreg is produced using a resin composition having a low dielectric constant (Dk) and dielectric loss tangent (Df), the dielectric constant (Dk) and dielectric loss tangent (Df) are sufficient as the whole prepreg due to the influence of the glass fiber substrate. It will not be low. For this reason, the present inventors have reduced the dielectric constant (Dk) and dielectric loss tangent (Df) of the prepreg as a whole by reducing the volume content of the glass fiber base based on the specific gravity relative to the prepreg. investigated. As a result of investigation, when the volume content based on the specific gravity of the resin composition with respect to the prepreg is increased, the thermal expansion coefficient is increased, and when a laminate such as a printed wiring board is produced by the prepreg, problems such as delamination between layers are caused. It became clear that this occurred. The present inventor has found that a predetermined amount of an inorganic filler is added to the prepreg in order to suppress an increase in the thermal expansion coefficient by increasing the volume content based on the specific gravity of the resin composition with respect to the prepreg. .

[Configuration of prepreg]
The prepreg according to Embodiment 1 of the present invention includes a resin composition having a dielectric constant (Dk) of 2.5 to 2.7 and a dielectric loss tangent (Df) of 0.005 to 0.007, and glass fiber. A base material and an inorganic filler are included. In the prepreg according to Embodiment 1 of the present invention, the glass fiber base based on the specific gravity is 5% by volume to 30% by volume, the resin composition is 45% by volume to 90% by volume, and the inorganic filler is 3% by volume to 35%. % By volume or less.

  The prepreg according to Embodiment 1 of the present invention includes, for example, a polyphenylene ether resin composition as a resin composition, and includes a polyphenylene ether cross-linking curing agent.

(Polyphenylene ether)
The polyphenylene ether contained in the resin composition constituting the prepreg according to the present invention is represented by the following general formula (1), and those having a number average molecular weight of 1000 or more and 7000 or less can be used.

In the general formula (1), X represents an aryl group, (Y) _m represents a polyphenylene ether moiety, and R ^{1 to} R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group. . In general formula (1), n is an integer from 1 to 6, and q is an integer from 1 to 4. Here, preferably, n is an integer of 1 or more and 4 or less, more preferably, n is 1 or 2, and ideally n is 1. Preferably, q is an integer of 1 or more and 3 or less, more preferably q is 1 or 2, and ideally q is 1.

(Aryl group)
As the aryl group in the general formula (1), an aromatic hydrocarbon group can be used. Specifically, a phenyl group, a biphenyl group, an indenyl group, and a naphthyl group can be used as the aryl group, and an aryl group is preferably used. Here, the aryl group includes a diphenyl ether group in which the aryl group is bonded with an oxygen atom, a benzophenone group bonded with a carbonyl group, or the like, a 2,2-diphenylpropane group bonded with an alkylene group, or the like. But you can. The aryl group may be substituted with a general substituent such as an alkyl group (preferably a C ₁ -C ₆ alkyl group, particularly a methyl group), an alkenyl group, an alkynyl group, or a halogen atom. However, since the “aryl group” is substituted on the polyphenylene ether moiety through an oxygen atom, the number of general substituents depends on the number of polyphenylene ether moieties.

(Polyphenylene ether part)
The polyphenylene ether moiety in the general formula (1) is represented by the following general formula (2) and consists of phenyloxy repeating units. Here, the phenyl group may be substituted with a general substituent.

In the above general formula (2), R ^{4 to} R ⁷ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an alkenylcarbonyl group. In General formula (2), m shows the integer of 1-100. Here, the value of m is adjusted so that the number average molecular weight of the polyphenylene ether of the general formula (1) is 1000 or more and 7000 or less. That is, m is not a fixed value but may be a variable within a certain range such that the number average molecular weight of the whole polyphenylene ether contained in the polyphenylene ether resin composition is 1000 or more and 7000 or less.

  Here, when the number average molecular weight of polyphenylene ether exceeds 7000, the fluidity at the time of shaping | molding falls and multilayer shaping | molding will become difficult. On the other hand, if the number average molecular weight of the polyphenylene ether is less than 1000, the original excellent dielectric properties and heat resistance of the polyphenylene ether resin may not be obtained. In order to obtain more excellent fluidity, heat resistance, and dielectric properties, the number average molecular weight of the polyphenylene ether is preferably 1200 or more and 5000 or less. More preferably, the polyphenylene ether has a number average molecular weight of 1500 or more and 4500 or less.

  The polyphenylene ether having the number average molecular weight described above has very good compatibility when blended with a crosslinking type curing agent. In other words, the lower the number average molecular weight of polyphenylene ether, the higher the compatibility with the mixture. Therefore, viscosity increase due to phase separation hardly occurs, and volatilization of the low molecular weight cross-linking curing agent is suppressed. As a result, the embedding property of the polyphenylene ether resin composition into a via hole or the like can be improved.

  As the alkyl group, alkenyl group, and alkynyl group in the general formula (2), those similar to the alkyl group, alkenyl group, and alkynyl group in the general formula (1) described below can be used. As the alkenylcarbonyl group of the polyphenylene ether moiety, a carbonyl group substituted with the above alkenyl group can be used. Specifically, an acryloyl group or a methacryloyl group can be used.

Here, the polyphenylene ether moiety in the general formula (2) is, for example, a vinyl group, a 2-propylene group (allyl group), a methacryloyl group, an acryloyl group, or a 2-propyne group (propargyl group) as the substituents R ^{4 to} R ⁷ . It may have an unsaturated hydrocarbon-containing group. By providing the unsaturated hydrocarbon-containing group in the substituents R ^{4 to} R ⁷ of the polyphenylene ether portion, a more remarkable effect of the cross-linking curing agent can be obtained.

  The polyphenylene ether having the above-mentioned group at the terminal has good interaction with the cross-linking curing agent. Therefore, the heat resistance can be improved only by adding a relatively small amount of the cross-linking curing agent, and a low dielectric constant can be realized.

(Alkyl group)
As the alkyl group in the general formula (1) and the general formula (2), a saturated hydrocarbon group can be used. Examples of the alkyl group may be performed using C ₁ -C ₁₀ alkyl group. Preferably, it is the use of C ₁ -C ₆ alkyl group as the alkyl group described above. More preferably, it may be used a C ₁ -C ₄ alkyl group as the alkyl group described above. More preferably, it may be used to C ₁ -C ₂ alkyl group as the alkyl group described above. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, or a hexyl group can be used as the alkyl group.

(Alkenyl group)
As the alkenyl group in the general formula (1) and the general formula (2), an unsaturated hydrocarbon group having at least one carbon-carbon double bond in the structure can be used. As the alkenyl group, a C ₂ -C ₁₀ alkenyl group may be used. Preferably, it is the use of C ₂ -C ₆ alkenyl group as an alkenyl group described above. More preferably, it is the use of C ₂ -C ₄ alkenyl group as an alkenyl group described above. Specifically, an ethylene group, a 1-propylene group, a 2-propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, or a hexylene group can be used as the alkenyl group.

(Alkynyl group)
As the alkynyl group in the general formula (1) and the general formula (2), an unsaturated hydrocarbon group having at least one carbon-carbon triple bond in the structure can be used. As the alkynyl group, a C ₂ -C ₁₀ alkynyl group may be used. Preferably, it is the use of C ₂ -C ₆ alkynyl group as an alkynyl group as described above. More preferably, it is the use of C ₂ -C ₄ alkynyl group as an alkynyl group as described above. Specifically, an ethyn group, a 1-propyne group, a 2-propyne group, an isopropyne group, a butyne group, an isobutyne group, a pentyne group, and a hexyne group can be used as the alkynyl group.

(Crosslinking curing agent)
As the crosslinkable curing agent contained in the resin composition, a curing agent that three-dimensionally crosslinks polyphenylene ether can be used. Specifically, a polyfunctional vinyl compound, a vinyl benzyl ether compound, an allyl ether compound, or a trialkenyl isocyanurate can be used as the crosslinking curing agent. Polyfunctional vinyl compounds include divinylbenzene, divinylnaphthalene, and divinylbiphenyl. Vinyl benzyl ether compounds are synthesized by the reaction of phenol and vinyl benzyl chloride. Allyl ether compounds are synthesized by the reaction of styrene monomer, phenol, and allyl chloride. Trialkenyl isocyanurate has good compatibility, and triallyl isocyanurate (hereinafter referred to as TAIC) or triallyl cyanurate (hereinafter referred to as TAC) can be used.

  In addition to the above materials, (meth) acrylate compounds (methacrylate compounds and acrylate compounds) can be used as the crosslinkable curing agent. In particular, a functional (meth) acrylate compound having 3 or more and 5 or less may be contained in an amount of 3 to 20 parts by mass with respect to 100 parts by mass of the total amount of the resin composition. Trimethylolpropane trimethacrylate (TMPT) or the like can be used as the functional methacrylate compound having 3 to 5 functional groups, while trimethylolpropane triacrylate or the like is used as the functional acrylate compound having 3 to 5 functional groups. Can do. By using the above-mentioned crosslinkable curing agent, the heat resistance of the resin composition can be further improved.

  When the functionality of the (meth) acrylate compound is less than 3 or more than 5, the heat resistance is lowered as compared with a (meth) acrylate compound having a functionality of 3 or more and 5 or less. Moreover, even if it is a (meth) acrylate compound having a functionality of 3 or more and 5 or less, when the content is less than 3 parts by mass with respect to 100 parts by mass of the total resin composition, the heat resistance of the resin composition is improved. The effect cannot be obtained sufficiently. On the other hand, when it exceeds 20 parts by mass, the dielectric properties and moisture resistance are lowered.

  The content ratio of the polyphenylene ether and the crosslinkable curing agent in the resin composition is preferably 30/70 or more and 90/10 or less. Preferably, the content ratio is 50/50 or more and 90/10 or less. More preferably, the content ratio is 60/40 or more and 90/10 or less.

  Here, if the content ratio of the polyphenylene ether is smaller than the lower limit, the rigidity of the entire resin composition is lowered. As a result, it becomes difficult to make the entire resin composition multilayer. On the other hand, when the content ratio of the polyphenylene ether is larger than the upper limit, the heat resistance of the entire resin composition is lowered. By adjusting the content ratio of the polyphenylene ether and the cross-linking curing agent to the above range, good fluidity and compatibility of the resin composition can be obtained. Therefore, the embedding property of the resin composition in a via hole or the like can be improved.

  In the prepreg of the present invention, the volume content based on the specific gravity of the resin composition is 45% by volume or more and 90% by volume or less.

(Glass fiber substrate)
As a glass fiber base material contained in the prepreg of the present invention, cloths such as E glass, D glass, S glass, T glass, NE glass, and quartz can be used. The thickness of the glass cloth is not particularly limited, but is used for laminated plate applications in the range of 0.01 to 0.2 mm. It is preferable from the viewpoint of stability. A glass cloth surface-treated with a silane coupling agent such as epoxy silane treatment or amino silane treatment is preferably used from the viewpoint of moisture absorption heat resistance. Examples of the glass fiber base material included in the prepreg of the present invention include E glass cloth such as IPC No. # 1037, IPC # 1067, IPC # 1078, IPC # 1080, IPC No. # 1280 and IPC No. # 3313. Although it can be used, it is not limited to these, The glass fiber base material which adapted the IPC standard specification can be selected suitably.

  In the prepreg of the present invention, the volume content based on the specific gravity of the glass fiber substrate is 5% by volume or more and 30% by volume or less. The prepreg of the present invention increases the volume content based on the specific gravity of the resin composition relative to the prepreg by setting the volume content based on the specific gravity of the glass fiber base to these ranges, and the dielectric constant of the entire prepreg (Dk) and dielectric loss tangent (Df) can be reduced.

(Inorganic filler)
The inorganic filler contained in the prepreg of the present invention can include, for example, silica, but is not limited thereto. As silica, for example, spherical synthetic silica can be used, and fine particles having an average particle size of 10 μm or less can be used. Here, the average particle diameter may be a value described in a material such as a catalog of the filler to be added, or may be an average value or a median value of a plurality of randomly extracted fillers. By setting the average particle size of the filler to the above condition, a prepreg having high smoothness and high reliability can be obtained. In the prepreg of the present invention, by adding silica to the prepreg, an increase in the coefficient of thermal expansion of the prepreg can be effectively suppressed. As a result, the dielectric constant (Dk) and dielectric loss tangent (Df) of the entire prepreg Can be reduced.

  In the prepreg of the present invention, the volume content based on the specific gravity of the inorganic filler is 3% by volume or more and 35% by volume or less. The prepreg of the present invention reduces the dielectric constant (Dk) and dielectric loss tangent (Df) of the entire prepreg and increases the thermal expansion coefficient by setting the volume content based on the specific gravity of the inorganic filler within these ranges. Can be suppressed.

(Other additives)
The resin composition of this invention can add the 1 or more additive selected from an unmodified polyphenylene ether, a flame retardant, and a reaction initiator as needed. Moreover, you may add the general additive component of the resin composition used for manufacture of electronic devices, such as a printed wiring board.

(Unmodified polyphenylene ether)
In addition to the above polyphenylene ether, the resin composition of the present invention may contain unmodified polyphenylene ether having a number average molecular weight of 9000 to 18000. By adding unmodified polyphenylene ether, it is possible to control the fluidity of the resin composition and improve the heat resistance. Moreover, precipitation of additional components, such as a filler, can be suppressed in a resin composition. Here, the unmodified polyphenylene ether is a polyphenylene ether having no carbon-carbon unsaturated group in the molecule, and the amount added is 100 parts by mass of the total mass of the polyphenylene ether and the cross-linking curing agent. 3 parts by mass or more and 70 parts by mass or less are preferable.

  In addition, styrene / butadiene block copolymers, styrene / isoprene block copolymers, 1,2-polybutadiene, 1,4-polybutadiene, maleic acid-modified polybutadiene, and acrylic acid-modified polybutadiene are used to improve heat resistance, adhesion, and dimensional stability. And one or more compatibilizers selected from epoxy-modified polybutadiene can be used.

(Flame retardants)
By adding a flame retardant to the resin composition, water resistance, moisture resistance, moisture absorption heat resistance, and glass transition point of a prepreg using the resin composition can be improved. As the flame retardant, a brominated organic compound such as an aromatic bromine compound can be used. Specifically, decabromodiphenylethane, 4,4-dibromobiphenyl, ethylenebistetrabromophthalimide, or the like can be used. Preferably, the brominated organic compound is contained in an amount such that the bromine content is 8 parts by mass or more and 20 parts by mass or less with respect to the total amount of the resin composition.

  When the bromine content is smaller than the lower limit, the flame retardancy of the prepreg is lowered, and the flame retardancy at the UL standard 94V-0 level cannot be maintained. On the other hand, when the bromine content is larger than the upper limit, bromine is easily dissociated when the prepreg is heated, and the heat resistance of the prepreg is lowered.

(Reaction initiator)
By adding a reaction initiator to the resin composition, a more remarkable effect of the cross-linking curing agent can be obtained. As the reaction initiator, any general material can be used as long as it can improve the properties such as heat resistance of the resin composition by promoting the curing of the resin composition at an appropriate temperature and time. Specifically, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, benzoyl peroxide 3,3 ′, 5,5′-tetramethyl-1,4-diphenoquinone, chloranil, 2,4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl monocarbonate, azobisisobutyronitrile An oxidizing agent such as can be used. Here, if necessary, a carboxylic acid metal salt or the like may be added to further accelerate the curing reaction.

  As described above, according to the prepreg according to Embodiment 1 of the present invention, the resin having a dielectric constant (Dk) of 2.5 or more and 2.7 or less and a dielectric loss tangent (Df) of 0.005 or more and 0.007 or less. Low Dk and low Df can be realized by including a predetermined amount of each of the composition, the glass fiber substrate, and the inorganic filler.

[Prepreg production method]
In the prepreg according to the present invention, a resin composition having a dielectric constant (Dk) of 2.5 or more and 2.7 or less and a dielectric loss tangent (Df) of 0.005 or more and 0.007 or less is used. it can. As the base material, a glass fiber base material can be used. For example, E glass cloth can be used. Moreover, in order to suppress the increase in the thermal expansion coefficient of the prepreg, silica is included as an inorganic filler. The varnish to be impregnated into the substrate includes a resin composition having a dielectric constant (Dk) of 2.5 to 2.7 and a dielectric loss tangent (Df) of 0.005 to 0.007, an inorganic filler, , At least.

  The amount of varnish impregnated into the base material is preferably such that the volume content based on the specific gravity of the resin in the prepreg is 45% by volume or more. Since the dielectric constant of the substrate is larger than the dielectric constant of the resin, in order to reduce the dielectric constant of the printed wiring board obtained using this prepreg, the volume content based on the specific gravity of the resin solid content in the prepreg is set as above. More than the value of. The base material impregnated with the varnish can be heated at a temperature of 80 ° C. or higher and 150 ° C. or lower for a period of 1 minute or longer and 10 minutes or shorter. However, the heating conditions of the base material impregnated with the varnish are not limited to the above conditions.

[Method for producing printed wiring board (laminate)]
Here, the manufacturing method of the laminated body using the prepreg produced as mentioned above is demonstrated. First, one or a plurality of prepregs are stacked, and a metal foil such as a copper foil is stacked on both upper and lower surfaces or one surface thereof, and the laminate is heated and pressed. By this molding, a laminate having metal foil on both sides or one side can be produced. A printed wiring board can be obtained by patterning and etching the metal foil of the laminate to form a circuit. Moreover, a multilayer printed wiring board can be produced by stacking a plurality of prepregs sandwiching the printed wiring board on which a circuit is formed, and performing heat-pressure molding.

The heating and pressing conditions vary depending on the content ratio of the raw material of the resin composition according to the present invention, but generally 170 ° C. or higher and 230 ° C. or lower, pressure 1.0 MPa or higher and 6.0 MPa or lower (10 kg / cm ² or higher and 60 kg). / Cm ² or less) is preferably heated and pressurized for an appropriate time.

  The metal foil used in the above laminate has a surface roughness (ten-point average roughness: Rz) of 2 μm or less, and a surface on the side where the resin layer is formed by the prepreg (surface on the side in contact with the prepreg) However, it is possible to use a copper foil that has been treated with zinc or a zinc alloy for rust prevention or improved adhesion to the resin layer and further subjected to a coupling treatment with a vinyl group-containing silane coupling agent or the like. Such a copper foil has good adhesion to the resin layer (insulating layer), and a printed wiring board having excellent high frequency characteristics can be obtained. In addition, when processing copper foil with zinc or a zinc alloy, zinc and a zinc alloy can be formed in the surface of copper foil by the plating method.

  Thus, the obtained laminated body and printed wiring board can implement | achieve low Dk and low Df. In addition, a laminate or a printed wiring board having high moldability, water resistance, moisture resistance, moisture absorption heat resistance, and glass transition point can be obtained.

<Embodiment 2>
Hereinafter, the prepreg according to the present invention will be described in detail. However, the prepreg of the present invention is not construed as being limited to the description of the following embodiments and examples.

[Configuration of prepreg]
The prepreg according to Embodiment 2 of the present invention includes a resin composition having a dielectric constant (Dk) of 2.5 to 2.7 and a dielectric loss tangent (Df) of 0.005 to 0.007, and glass fiber. A base material and an inorganic filler are included. In the prepreg according to Embodiment 2 of the present invention, the glass fiber base based on specific gravity is 5% by volume to 30% by volume, the resin composition is 45% by volume to 90% by volume, and the inorganic filler is 3% by volume to 35%. % By volume or less. The prepreg according to Embodiment 2 of the present invention contains an epoxy compound, a polyphenylene ether, a cyanate ester compound, a curing catalyst, and a halogen flame retardant. The epoxy compound has a number average molecular weight of 1000 or less and does not contain a halogen atom having at least two epoxy groups in one molecule. The polyphenylene ether has a number average molecular weight of 5000 or less. The curing catalyst promotes the reaction between the epoxy compound and polyphenylene ether and the cyanate ester compound that is a curing agent.

(Epoxy compound)
As the epoxy compound, a dicyclopentadiene type epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a phenol novolac type epoxy compound, a naphthalene type epoxy compound, a biphenyl type epoxy compound, or the like can be used. These can be used alone or in combination. Of these, dicyclopentadiene type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, and biphenyl type epoxy compounds are particularly preferred because of their good compatibility with polyphenylene ether. In addition, although it is preferable not to contain a halogenated epoxy compound in this resin composition, as long as the effect of this invention is not impaired, you may add as needed.

  It is preferable that the content rate of the epoxy compound in the prepreg of this embodiment is 20 mass parts or more and 60 mass parts or less with respect to 100 mass parts of total amounts of the component of an epoxy compound, polyphenylene ether, and a cyanate ester compound. More preferably, the content ratio of the epoxy compound is 30 parts by mass or more and 50 parts by mass or less. By making the content rate of an epoxy compound into said range, sufficient heat resistance and the outstanding mechanical characteristic and electrical property can be maintained.

(Polyphenylene ether)
The polyphenylene ether has a number average molecular weight of 5000 or less, preferably 2000 or more and 4000 or less.

  When the number average molecular weight of the polyphenylene ether exceeds 5000, the fluidity is deteriorated and the reactivity with the epoxy group is also lowered. Therefore, it takes a long time for the curing reaction, and it is not taken into the curing system, and unreacted ones increase, the glass transition temperature decreases, and sufficient heat resistance cannot be obtained.

  The content ratio of the polyphenylene ether in the prepreg of the present embodiment is preferably 20 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the total amount of the components of the epoxy compound, the polyphenylene ether, and the cyanate ester compound. More preferably, the content of polyphenylene ether is 20 to 40 parts by mass. When the content ratio of the polyphenylene ether is within the above range, excellent dielectric properties can be obtained.

(Cyanate ester compound)
As the cyanate ester compound, a compound having two or more cyanate groups in one molecule can be used. Specifically, 2,2-bis (4-cyanatophenyl) propane, bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) ethane, etc. Alternatively, aromatic cyanate ester compounds such as derivatives thereof can be used. These can be used alone or in combination.

  The cyanate ester compound is a component that acts as a curing agent for the epoxy compound for forming the epoxy resin and forms a rigid skeleton. Therefore, a high glass transition point (Tg) can be obtained. Moreover, since the viscosity is low, the high fluidity of the resin varnish obtained can be maintained.

  The content ratio of the cyanate ester compound in the prepreg of the present embodiment is 20 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the total amount of the components of the epoxy compound, polyphenylene ether, and cyanate ester compound. preferable. More preferably, the content ratio of the cyanate ester compound is 20 parts by mass or more and 40 parts by mass or less. When the content ratio of the cyanate ester compound is in the above range, sufficient heat resistance can be obtained, the impregnation with respect to the substrate is excellent, and crystals can be hardly precipitated even in the resin varnish.

(Curing catalyst)
Examples of curing catalysts include octanoic acid, stearic acid, acetylacetonate, naphthenic acid, organic acid salts such as salicylic acid, organic metal salts such as Zn, Cu, and Fe, tertiary amines such as triethylamine and triethanolamine, 2-ethyl- Imidazoles such as 4-imidazole and 4-methylimidazole can be used. These can be used alone or in combination. Among the above, organic metal salts, particularly zinc octoate is preferable because higher heat resistance can be obtained.

  The content of the curing catalyst in the prepreg of the present embodiment is, for example, 0.005 with respect to the total amount (100 parts by mass) of the components of the epoxy compound, polyphenylene ether, and cyanate ester compound when using an organic metal salt. It can be set to 5 parts by mass or more. For example, when imidazoles are used, the content of the curing catalyst is 0.01 parts by mass or more and 5 parts by mass with respect to the total amount (100 parts by mass) of the components of the epoxy compound, polyphenylene ether, and cyanate ester compound. It can be as follows.

  In the prepreg of the present invention, the volume content based on the specific gravity of the resin composition is 45% by volume or more and 90% by volume or less.

(Halogen flame retardant)
As the halogen-based flame retardant, a halogen-based flame retardant that does not dissolve in a varnish adjusted with a solvent such as toluene can be used. Specifically, as the halogen-based flame retardant, ethylene dipentabromobenzene, ethylene bistetrabromophthalimide, decabromodiphenyl oxide, tetradecabromodiphenoxybenzene, bis (tribromophenoxy) ethane, or the like can be used. Of these, ethylenedipentabromobenzene, ethylenebistetrabromophthalimide, decabromodiphenyl oxide, and tetradecabromodiphenoxybenzene have a melting point of 300 ° C. or higher and high heat resistance, so that the heat resistance of the prepreg is improved. Can do. When a halogen-based flame retardant having a melting point of 300 ° C. or higher and high heat resistance can be used, it is possible to suppress the elimination of halogen at a high temperature, and thus it is possible to suppress a decrease in heat resistance due to decomposition of the cured product.

  The average particle diameter in the dispersed state of the halogen-based flame retardant is 0.1 μm or more and 50 μm or less, and more preferably 1 μm or more and 10 μm or less can sufficiently maintain heat resistance and interlayer insulation. The average particle size can be measured with a particle size distribution meter (SALD-2100) manufactured by Shimadzu Corporation.

  The content ratio of the halogen-based flame retardant in the prepreg of the present embodiment is such that the halogen concentration is 5 parts by mass or more and 30 parts by mass or less in 100 parts by mass of the total amount of resin components (that is, components excluding inorganic components) in the obtained cured product. It is preferable to make it contain in such a ratio.

(Glass fiber substrate)
As a glass fiber base material contained in the prepreg of the present invention, cloths such as E glass, D glass, S glass, T glass, NE glass, and quartz can be used. The thickness of the glass cloth is not particularly limited, but is used for laminated plate applications in the range of 0.01 to 0.2 mm. It is preferable from the viewpoint of stability. A glass cloth surface-treated with a silane coupling agent such as epoxy silane treatment or amino silane treatment is preferably used from the viewpoint of moisture absorption heat resistance. Examples of the glass fiber base material included in the prepreg of the present invention include E glass cloth such as IPC No. # 1037, IPC # 1067, IPC # 1078, IPC # 1080, IPC No. # 1280 and IPC No. # 3313. Although it can be used, it is not limited to these, The glass fiber base material which adapted the IPC standard specification can be selected suitably.

  In the prepreg of the present invention, the volume content based on the specific gravity of the glass fiber substrate is 5% by volume or more and 30% by volume or less. The prepreg of the present invention increases the volume content based on the specific gravity of the resin composition relative to the prepreg by setting the volume content based on the specific gravity of the glass fiber base to these ranges, and the dielectric constant of the entire prepreg (Dk) and dielectric loss tangent (Df) can be reduced.

(Inorganic filler)
The inorganic filler contained in the prepreg of the present invention can include, for example, silica, but is not limited thereto. As silica, for example, spherical synthetic silica can be used, and fine particles having an average particle size of 10 μm or less can be used. Here, the average particle diameter may be a value described in a material such as a catalog of the filler to be added, or may be an average value or a median value of a plurality of randomly extracted fillers. By setting the average particle size of the filler to the above condition, a prepreg having high smoothness and high reliability can be obtained. In the prepreg of the present invention, by adding silica to the prepreg, an increase in the coefficient of thermal expansion of the prepreg can be effectively suppressed. As a result, the dielectric constant (Dk) and dielectric loss tangent (Df) of the entire prepreg Can be reduced.

  In the prepreg of the present invention, the volume content based on the specific gravity of the inorganic filler is 3% by volume or more and 35% by volume or less. The prepreg of the present invention reduces the dielectric constant (Dk) and dielectric loss tangent (Df) of the entire prepreg and increases the thermal expansion coefficient by setting the volume content based on the specific gravity of the inorganic filler within these ranges. Can be suppressed.

  In addition to the above inorganic filler, the resin composition of the present invention may be added with general additive components of resin compositions used in the manufacture of electronic devices such as printed wiring boards. For example, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a flame retardant, a dye, a pigment, a lubricant and the like may be added.

(Other additives)
If necessary, the resin composition of the present invention may contain one or more additives selected from unmodified polyphenylene ether and a reaction initiator. Moreover, you may add the general additive component of the resin composition used for manufacture of electronic devices, such as a printed wiring board. Since the unmodified polyphenylene ether and the reaction initiator have been described in the first embodiment, detailed description thereof will be omitted.

  As described above, according to the prepreg according to the second embodiment of the present invention, the resin having a dielectric constant (Dk) of 2.5 or more and 2.7 or less and a dielectric loss tangent (Df) of 0.005 or more and 0.007 or less. Low Dk and low Df can be realized by including a predetermined amount of each of the composition, the glass fiber substrate, and the inorganic filler.

[Prepreg production method]
In the present resin composition of the prepreg according to the second embodiment of the present invention, the components of the epoxy compound, polyphenylene ether, and cyanate ester compound are all dissolved in the resin varnish, and the components of the inorganic filler are: It is not dissolved in the resin varnish but is dispersed. Such a resin varnish is prepared as follows, for example.

  First, a predetermined amount of an epoxy compound and a cyanate ester compound are dissolved in a resin solution of polyphenylene ether. This dissolution may be performed at room temperature or while heating. As an epoxy compound and a cyanate ester compound, the formation of precipitates in the resin varnish can be suppressed by using a material that dissolves in a solvent such as toluene at room temperature.

  Here, when an inorganic filler is added as an additive, a resin varnish is prepared by dispersing the filler until a predetermined dispersion state is obtained using a ball mill, a bead mill, a planetary mixer, a roll mill, etc. Is done.

  A prepreg can be obtained by impregnating the substrate with the resin varnish obtained as described above and drying it by the same production method as in Embodiment 1. Moreover, a printed wiring board (laminated body) can be obtained by the same manufacturing method as in the first embodiment.

  Below, the prepreg which concerns on Embodiment 1 and Embodiment 2 of this invention is produced, and the result of having evaluated the characteristic value of dielectric constant (Dk) and dielectric loss tangent (Df) is demonstrated concretely. Examples 1 to 6 shown below correspond to the examples of the first embodiment, and examples 7 to 12 correspond to the examples of the second embodiment.

  First, the polyphenylene ether used in Examples 1 to 6 and Comparative Examples 1 to 2 will be described.

(Polyphenylene ether (1))
CuBr ₂ 3.88 g (17.4 mmol), N, N′-di-t-butylethylenediamine 0.75 g (4.) in a 12-liter vertical reactor equipped with a stirrer, thermometer, air introduction tube and baffle plate. 4 mmol), 28.04 g (277.6 mmol) of n-butyldimethylamine, and 2600 g of toluene, stirred at a reaction temperature of 40 ° C., and dissolved in 2300 g of methanol in advance, 2,2 ′, 3,3 ′, 5,5′-hexamethyl- (1,1′-biphenol) -4,4′-diol 129.3 g (0.48 mol), 2,6-dimethylphenol 233.7 g (1.92 mol), 2,3, 6-trimethylphenol 64.9 g (0.48 mol), N, N′-di-t-butylethylenediamine 0.51 g (2.9 mmol), n-butyldimethyl A mixed gas of 10.90 g (108.0 mmol) of tilamine was added dropwise over 230 minutes while bubbling at a flow rate of 5.2 liters / min with a mixed gas adjusted to an oxygen concentration of 8% by mixing nitrogen and air. And stirring was performed.

  After completion of the dropwise addition, 1500 g of water in which 19.89 g (52.3 mmol) of ethylenediaminetetraacetic acid tetrasodium was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with a 1N hydrochloric acid aqueous solution and then with pure water. The obtained solution was concentrated to 50 wt% with an evaporator to obtain 836.5 g of a toluene solution of a bifunctional phenylene ether oligomer (resin “A”). The resin “A” had a number average molecular weight of 986, a weight average molecular weight of 1530, and a hydroxyl group equivalent of 471.

  In a reactor equipped with a stirrer, a thermometer, and a reflux tube, 836.5 g of a toluene solution of resin “A”, vinylbenzyl chloride (trade name CMS-P; manufactured by Seimi Chemical Co., Ltd.) 162.6 g, methylene chloride 1600 g, 12.95 g of benzyldimethylamine, 420 g of pure water, and 178.0 g of a 30.5 wt% NaOH aqueous solution were charged, followed by stirring at a reaction temperature of 40 ° C. After stirring for 24 hours, the organic layer was washed with a 1N aqueous hydrochloric acid solution and then with pure water. The obtained solution was concentrated with an evaporator, dropped into methanol for solidification, and the solid was collected by filtration and vacuum dried to obtain 503.5 g of “polyphenylene ether (1)”. The number average molecular weight of “polyphenylene ether (1)” was 1187, the weight average molecular weight was 1,675, and the vinyl group equivalent was 590 g / vinyl group.

(Polyphenylene ether (2))
CuBr ₂ (9.36 g, 42.1 mmol) and N, N′-di-t-butylethylenediamine (1.81 g) in a 12-liter vertical reactor equipped with a stirrer, thermometer, air inlet tube and baffle plate (10. 5 mmol), 67.77 g (671.0 mmol) of n-butyldimethylamine, and 2600 g of toluene, stirred at a reaction temperature of 40 ° C., and dissolved in 2300 g of methanol in advance, 2,2 ′, 3,3 ′, 5,5′-hexamethyl- (1,1′-biphenol) -4,4′-diol 129.32 g (0.48 mol), 2,6-dimethylphenol 878.4 g (7.2 mol), N, N ′ -A mixed solution of 1.22 g (7.2 mmol) of di-t-butylethylenediamine and 26.35 g (260.9 mmol) of n-butyldimethylamine The hydrogen mixed gas with an air are mixed and adjusted to an oxygen concentration of 8% 5.2 l / min flow rate 230 minutes over while bubbling with the dropwise, the mixture was stirred.

  After completion of the dropping, 1500 g of water in which 48.06 g (126.4 mmol) of ethylenediaminetetraacetic acid tetrasodium was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with a 1N hydrochloric acid aqueous solution and then with pure water. The obtained solution was concentrated to 50 wt% with an evaporator to obtain 1981 g of a toluene solution of a bifunctional phenylene ether oligomer (resin “B”). The resin “B” had a number average molecular weight of 1975, a weight average molecular weight of 3514, and a hydroxyl group equivalent of 990.

  In a reactor equipped with a stirrer, a thermometer, and a reflux tube, 833.4 g of a toluene solution of the resin “B”, 76.7 g of vinylbenzyl chloride (trade name CMS-P; manufactured by Seimi Chemical Co., Ltd.), 1600 g of methylene chloride, 6.2 g of benzyldimethylamine, 199.5 g of pure water, and 83.6 g of a 30.5 wt% NaOH aqueous solution were charged and stirred at a reaction temperature of 40 ° C. After stirring for 24 hours, the organic layer was washed with a 1N aqueous hydrochloric acid solution and then with pure water. The obtained solution was concentrated with an evaporator, dropped into methanol for solidification, and the solid was collected by filtration and vacuum dried to obtain 450.1 g of “polyphenylene ether (2)”. The number average molecular weight of vinyl “polyphenylene ether (2)” was 2250, the weight average molecular weight was 3920, and the vinyl group equivalent was 1189 g / vinyl group.

  Next, the manufacturing method of the prepreg of Example 1 thru | or Example 6, and Comparative Examples 1 and 2, and the evaluation sample of a dielectric constant and a dielectric loss tangent is demonstrated.

[Example 1]
70 parts by mass of the above polyphenylene ether (1) was prepared, 100 parts by mass of toluene was added as a solvent, and the mixture was stirred at 80 ° C. for 30 minutes and completely dissolved. 30 parts by mass of “TAIC” manufactured by Nippon Kasei Co., Ltd. as a crosslinkable curing agent and ethylene bis (pentabromophenyl) (Albemarle) as a brominated organic compound as a flame retardant are used for the polyphenylene ether solution thus obtained. 20 parts by mass of “SAYTEX 8010 (trade name)” manufactured by Japan Corporation and 10 parts by mass of spherical synthetic silica (“SC2050 (trade name)” manufactured by Admatechs Co., Ltd.) as an inorganic filler were blended. These were mixed, dispersed, and dissolved in toluene as a solvent and diluted to a solid content of 65% to obtain a varnish of a resin composition. Since the above flame retardant is a brominated organic compound that is non-reactive with polyphenylene ether and TAIC, the flame retardant was not dissolved in toluene but dispersed in the varnish as the resin composition.

Next, IPC No. After impregnating the above varnish using # 1280 E glass cloth, it was dried by heating at a temperature of 170 ° C. for 5 minutes, the solvent was removed and the resin composition was 71 vol%, and the inorganic filler was 4 vol. %, And a prepreg having a glass fiber substrate content of 25% by volume was obtained. Eight prepregs thus obtained were stacked, and 18 μm thick copper foil (3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.) was stacked on both upper and lower sides thereof. Temperature 210 ° C., pressure 3.0 MPa (3
0 kg / cm ² ) for 150 minutes under heat and pressure to obtain a double-sided copper-clad laminate for a printed wiring board having a thickness of 0.8 mm. Next, using the obtained test piece from which the copper foil of the copper-clad laminate having a thickness of 0.8 mm was removed, the dielectric constant and dielectric loss tangent of 10 GHz were obtained by the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies). Was measured.

[Example 2]
In Example 2, instead of the base material used in Example 1, IPC No. A # 1037 E glass cloth was used to prepare a prepreg having a resin composition of 87% by volume, an inorganic filler of 5% by volume, and a glass fiber substrate of 8% by volume. In addition, the manufacturing method of the varnish of Example 2 was performed by the method similar to Example 1. FIG. Moreover, the preparation method of the prepreg of Example 2 was performed like Example 1 except said point.

[Example 3]
In Example 3, 70 parts by mass of the above polyphenylene ether (1) was prepared, 100 parts by mass of toluene was added as a solvent, and the mixture was stirred at 80 ° C. for 30 minutes and completely dissolved. 30 parts by mass of “TAIC” manufactured by Nippon Kasei Co., Ltd. as a crosslinkable curing agent and ethylene bis (pentabromophenyl) (Albemarle) as a brominated organic compound as a flame retardant are used for the polyphenylene ether solution thus obtained. 20 parts by mass of “SAYTEX 8010 (trade name)” manufactured by Japan Corporation and 50 parts by mass of spherical synthetic silica (“SC2050 (trade name)” manufactured by Admatechs Co., Ltd.) as an inorganic filler were blended. These were mixed, dispersed, and dissolved in toluene as a solvent and diluted to a solid content of 65% to obtain a varnish of a resin composition. Since the above flame retardant is a brominated organic compound that is non-reactive with polyphenylene ether and TAIC, the flame retardant was not dissolved in toluene but dispersed in the varnish as the resin composition.

Next, using varnish as a base material, IPC No. After impregnating the above varnish using # 3313 E glass cloth, it was dried by heating at a temperature of 170 ° C. for 5 minutes, the solvent was removed, the resin composition was 57 vol%, and the inorganic filler was 16 vol. %, And a prepreg having a glass fiber base material of 27% by volume was obtained. Eight prepregs thus obtained were stacked, and 18 μm thick copper foil (3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.) was stacked on both upper and lower sides thereof. 2. Temperature 210 ° C, pressure 3.
Heating and pressing were performed under molding conditions of 0 MPa (30 kg / cm ² ) for 150 minutes to obtain a double-sided copper-clad laminate for a printed wiring board having a thickness of 0.8 mm. Next, using the obtained test piece from which the copper foil of the copper-clad laminate having a thickness of 0.8 mm was removed, the dielectric constant and dielectric loss tangent of 10 GHz were obtained by the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies). Was measured.

[Example 4]
In Example 4, 70 parts by mass of the above polyphenylene ether (2) was prepared, 100 parts by mass of toluene was added as a solvent, and the mixture was stirred at 80 ° C. for 30 minutes and completely dissolved. 30 parts by mass of “TAIC” manufactured by Nippon Kasei Co., Ltd. as a crosslinkable curing agent and ethylene bis (pentabromophenyl) (Albemarle) as a brominated organic compound as a flame retardant are used for the polyphenylene ether solution thus obtained. 20 parts by mass of “SAYTEX 8010 (trade name)” manufactured by Japan Corporation and 50 parts by mass of spherical synthetic silica (“SC2050 (trade name)” manufactured by Admatechs Co., Ltd.) as an inorganic filler were blended. These were mixed, dispersed, and dissolved in toluene as a solvent and diluted to a solid content of 65% to obtain a varnish of a resin composition. Since the above flame retardant is a brominated organic compound that is non-reactive with polyphenylene ether and TAIC, the flame retardant was not dissolved in toluene but dispersed in the varnish as the resin composition.

Next, IPC No. After impregnating the above varnish using # 1037 E glass cloth, it was dried by heating at a temperature of 170 ° C. for 5 minutes, the solvent was removed, the resin composition was 71 vol%, and the inorganic filler was 20 vol. %, A prepreg having a glass fiber base material of 9% by volume was obtained. Eight prepregs thus obtained were stacked, and 18 μm thick copper foil (3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.) was stacked on both upper and lower sides thereof. Temperature 210 ° C., pressure 3.0 MPa (3
0 kg / cm ² ) for 150 minutes under heat and pressure to obtain a double-sided copper-clad laminate for a printed wiring board having a thickness of 0.8 mm. Next, using the obtained test piece from which the copper foil of the copper-clad laminate having a thickness of 0.8 mm was removed, the dielectric constant and dielectric loss tangent of 10 GHz were obtained by the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies). Was measured.

[Example 5]
In Example 5, 70 parts by mass of the above polyphenylene ether (2) was prepared, 100 parts by mass of toluene was added as a solvent, and the mixture was stirred at 80 ° C. for 30 minutes and completely dissolved. 30 parts by mass of “TAIC” manufactured by Nippon Kasei Co., Ltd. as a crosslinkable curing agent and ethylene bis (pentabromophenyl) (Albemarle) as a brominated organic compound as a flame retardant are used for the polyphenylene ether solution thus obtained. 20 parts by mass of “SAYTEX 8010 (trade name)” manufactured by Japan Corporation and 100 parts by mass of spherical synthetic silica (“SC2050 (trade name)” manufactured by Admatechs Co., Ltd.) as an inorganic filler were blended. These were mixed, dispersed, and dissolved in toluene as a solvent and diluted to a solid content of 65% to obtain a varnish of a resin composition. Since the above flame retardant is a brominated organic compound that is non-reactive with polyphenylene ether and TAIC, the flame retardant was not dissolved in toluene but dispersed in the varnish as the resin composition.

Next, IPC No. After impregnating the above varnish using E glass cloth of # 3313, it was dried by heating at a temperature of 170 ° C. for 5 minutes, the solvent was removed and the resin composition was 49% by volume, and the inorganic filler was 27% by volume. %, And a prepreg having a glass fiber substrate content of 25% by volume was obtained. Eight prepregs thus obtained were stacked, and 18 μm thick copper foil (3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.) was stacked on both upper and lower sides thereof. Heating and pressing were performed under the molding conditions of a temperature of 210 ° C. and a pressure of 3.0 MPa (30 kg / cm ² ) for 150 minutes to obtain a double-sided copper-clad laminate for a printed wiring board having a thickness of 0.8 mm. Next, using the obtained test piece from which the copper foil of the copper-clad laminate having a thickness of 0.8 mm was removed, the dielectric constant and dielectric loss tangent of 10 GHz were obtained by the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies). Was measured.

[Example 6]
In Example 6, instead of the base material used in Example 5, IPC No. A # 1037 E glass cloth was used to prepare a prepreg having a resin composition of 61% by volume, an inorganic filler of 33% by volume, and a glass fiber substrate of 6% by volume. In addition, the manufacturing method of the varnish of Example 2 was performed by the method similar to Example 1. FIG. Moreover, the preparation method of the prepreg of Example 2 was performed like Example 1 except said point.

[Comparative Example 1]
In Comparative Example 1, which is a comparative example of Examples 1 to 3, the varnish of Example 3 was used, and IPC No. 4 was used as the base material. After impregnating the varnish of Example 3 using E glass cloth of # 3313, it was dried by heating at a temperature of 170 ° C. for 5 minutes, the solvent was removed, the resin composition was 54% by volume, and the inorganic filler was A prepreg of 15% by volume and 31% by volume of the glass fiber substrate was obtained. Eight prepregs thus obtained were stacked, and 18 μm thick copper foil (3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.) was stacked on both upper and lower sides thereof. Temperature 210 ° C., pressure 3.0 MPa (30
kg / cm ² ) for 150 minutes under heat and pressure to obtain a double-sided copper-clad laminate for a printed wiring board having a thickness of 0.8 mm. Next, using the obtained test piece from which the copper foil of the copper-clad laminate having a thickness of 0.8 mm was removed, the dielectric constant and dielectric loss tangent of 10 GHz were obtained by the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies). Was measured.

[Comparative Example 2]
In Comparative Example 2, which is a comparative example of Examples 4 to 6, the varnish of Example 4 was used, and IPC No. 4 was used as the base material. After impregnating the varnish of Example 4 using E glass cloth of # 2116, it was dried by heating at a temperature of 170 ° C. for 5 minutes, the solvent was removed, the resin composition was 45% by volume, and the inorganic filler was A prepreg having 12% by volume and 43% by volume of a glass fiber substrate was obtained. Eight prepregs thus obtained were stacked, and 18 μm thick copper foil (3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.) was stacked on both upper and lower sides thereof. Temperature 210 ° C., pressure 3.0 MPa (30
kg / cm ² ) for 150 minutes under heat and pressure to obtain a double-sided copper-clad laminate for a printed wiring board having a thickness of 0.8 mm. Next, using the obtained test piece from which the copper foil of the copper-clad laminate having a thickness of 0.8 mm was removed, the dielectric constant and dielectric loss tangent of 10 GHz were obtained by the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies). Was measured.

  FIG. 1 shows configurations and evaluation results of Examples 1 to 6 and Comparative Examples 1 and 2.

  As shown in FIG. 1, a resin composition having a dielectric constant (Dk) of 2.5 or more and 2.7 or less and a dielectric loss tangent (Df) of 0.005 or more and 0.007 or less, a glass fiber substrate, An inorganic filler, and a glass fiber substrate based on a specific gravity of 5% by volume to 30% by volume, a resin composition of 45% by volume to 90% by volume, and an inorganic filler of 3% by volume to 35% by volume. In Examples 1 to 6, it was confirmed that smaller Dk values and Df values can be obtained as compared with Comparative Examples 1 and 2 deviating from the volume content.

  Subsequently, the polyphenylene ether and the epoxy compound used in Examples 7 to 12 and Comparative Examples 3 to 4 will be described.

(Polyphenylene ether (3))
As the “polyphenylene ether (3)”, polyphenylene ether (SA90 manufactured by SABIC Innovative Plastics) having a hydroxyl group at the end of polyphenylene ether was used. The weight average molecular weight of “polyphenylene ether (3)” is 1700.

(Epoxy compound (1))
As the epoxy compound, a dicyclopentadiene type epoxy compound (“Epiclon HP7200 (trade name)” manufactured by DIC) was used. Epicron HP7200 has a number average molecular weight of 550.

(Epoxy compound (2))
As the epoxy compound, a naphthalene skeleton modified epoxy resin (“Epiclon HP4032D (trade name)” manufactured by DIC Company) was used. Epicron HP4032D has a number average molecular weight of 280.

  Next, a method for producing prepregs, dielectric constant and dielectric loss tangent evaluation samples of Examples 7 to 12 and Comparative Examples 3 to 4 will be described.

[Example 7]
30 parts by mass of the above polyphenylene ether (3) was prepared, toluene was added as a solvent, mixed and stirred, and completely dissolved. With respect to the polyphenylene ether solution thus obtained, 45 parts by mass of the above epoxy compound (1) and 2,2-bis (4-cyanatophenyl) propane (Mitsubishi Gas Chemical) as a cyanate ester compound were used. After adding 25 parts by mass of “CA210 (trade name)” manufactured by Co., Ltd., it was stirred for 30 minutes and completely dissolved. Furthermore, 25 parts by mass of the above-mentioned “SAYTEX8010” as a flame retardant and 10 parts by mass of the “SC2050” as an inorganic filler were added and dispersed with a ball mill to obtain a resin varnish. In addition, said flame retardant did not melt | dissolve but was disperse | distributed with the average particle diameter of 1 micrometer or more and 10 micrometers or less in the resin varnish.

Next, IPC No. After impregnating the above varnish using # 1280 E glass cloth, it was dried by heating at a temperature of 170 ° C. for 5 minutes, the solvent was removed, the resin composition was 70% by volume, and the inorganic filler was 4 volumes. %, And a prepreg having a glass fiber substrate content of 26% by volume was obtained. Eight prepregs thus obtained were stacked, and 18 μm thick copper foil (3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.) was stacked on both upper and lower sides thereof. Temperature 210 ° C., pressure 3.0 MPa (3
0 kg / cm ² ) for 150 minutes under heat and pressure to obtain a double-sided copper-clad laminate for a printed wiring board having a thickness of 0.8 mm. Next, using the obtained test piece from which the copper foil of the copper-clad laminate having a thickness of 0.8 mm was removed, the dielectric constant and dielectric loss tangent of 10 GHz were obtained by the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies). Was measured.

[Example 8]
In Example 8, instead of the base material used in Example 7, IPC No. Using a # 1037 E glass cloth, a prepreg having a resin composition of 86% by volume, an inorganic filler of 5% by volume, and a glass fiber substrate of 9% by volume was produced. In addition, the manufacturing method of the varnish of Example 8 was performed by the method similar to Example 7. FIG. The method for producing the prepreg of Example 8 was performed in the same manner as Example 1 except for the above points.

[Example 9]
In Example 9, 30 parts by mass of the above polyphenylene ether (3) was prepared, and toluene was added as a solvent, mixed and stirred to be completely dissolved. With respect to the polyphenylene ether solution thus obtained, 45 parts by mass of the above epoxy compound (1) and 2,2-bis (4-cyanatophenyl) propane (Mitsubishi Gas Chemical) as a cyanate ester compound were used. After adding 25 parts by mass of “CA210 (trade name)” manufactured by Co., Ltd., it was stirred for 30 minutes and completely dissolved. Furthermore, 25 parts by mass of the above-mentioned “SAYTEX8010” as a flame retardant and 50 parts by mass of the “SC2050” as an inorganic filler were added and dispersed with a ball mill to obtain a resin varnish. In addition, said flame retardant did not melt | dissolve but was disperse | distributed with the average particle diameter of 1 micrometer or more and 10 micrometers or less in the resin varnish.

Next, IPC No. After impregnating the above varnish using # 3313 E glass cloth, it was dried by heating at a temperature of 170 ° C. for 5 minutes, the solvent was removed and the resin composition was 55 vol%, and the inorganic filler was 17 vol. %, And a prepreg having a glass fiber base material of 27% by volume was obtained. Eight prepregs thus obtained were stacked, and 18 μm thick copper foil (3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.) was stacked on both upper and lower sides thereof. Heating and pressing were performed under the molding conditions of a temperature of 210 ° C. and a pressure of 3.0 MPa (30 kg / cm ² ) for 150 minutes to obtain a double-sided copper-clad laminate for a printed wiring board having a thickness of 0.8 mm. Next, using the obtained test piece from which the copper foil of the copper-clad laminate having a thickness of 0.8 mm was removed, the dielectric constant and dielectric loss tangent of 10 GHz were obtained by the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies). Was measured.

[Example 10]
In Example 10, the epoxy compound (2) was used in place of the epoxy compound (1). 30 parts by mass of the above polyphenylene ether (3) was prepared, toluene was added as a solvent, mixed and stirred, and completely dissolved. With respect to the polyphenylene ether solution thus obtained, 45 parts by mass of the above epoxy compound (2) and 2,2-bis (4-cyanatophenyl) propane (Mitsubishi Gas Chemical) as a cyanate ester compound were used. After adding 25 parts by mass of “CA210 (trade name)” manufactured by Co., Ltd., it was stirred for 30 minutes and completely dissolved. Furthermore, 25 parts by mass of the above-mentioned “SAYTEX8010” as a flame retardant and 50 parts by mass of the “SC2050” as an inorganic filler were added and dispersed with a ball mill to obtain a resin varnish. In addition, said flame retardant did not melt | dissolve but was disperse | distributed with the average particle diameter of 1 micrometer or more and 10 micrometers or less in the resin varnish.

Next, IPC No. After impregnating the above varnish using # 1037 E glass cloth, it was dried by heating at a temperature of 170 ° C. for 5 minutes, the solvent was removed, the resin composition was 70 vol%, and the inorganic filler was 21 vol. %, A prepreg having a glass fiber base material of 9% by volume was obtained. Eight prepregs thus obtained were stacked, and 18 μm thick copper foil (3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.) was stacked on both upper and lower sides thereof. Temperature 210 ° C., pressure 3.0 MPa (3
0 kg / cm ² ) for 150 minutes under heat and pressure to obtain a double-sided copper-clad laminate for a printed wiring board having a thickness of 0.8 mm. Next, using the obtained test piece from which the copper foil of the copper-clad laminate having a thickness of 0.8 mm was removed, the dielectric constant and dielectric loss tangent of 10 GHz were obtained by the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies). Was measured.

[Example 11]
In Example 11, 30 parts by mass of the above polyphenylene ether (3) was prepared, and toluene was added as a solvent, mixed and stirred to be completely dissolved. With respect to the polyphenylene ether solution thus obtained, 45 parts by mass of the above epoxy compound (2) and 2,2-bis (4-cyanatophenyl) propane (Mitsubishi Gas Chemical) as a cyanate ester compound were used. After adding 25 parts by mass of “CA210 (trade name)” manufactured by Co., Ltd., it was stirred for 30 minutes and completely dissolved. Further, 25 parts by mass of the above-mentioned “SAYTEX8010” as a flame retardant and 100 parts by mass of the “SC2050” as an inorganic filler were added and dispersed with a ball mill to obtain a resin varnish. In addition, said flame retardant did not melt | dissolve but was disperse | distributed with the average particle diameter of 1 micrometer or more and 10 micrometers or less in the resin varnish.

Next, IPC No. After impregnating the above varnish using # 3313 E glass cloth, it was dried by heating at a temperature of 170 ° C. for 5 minutes, the solvent was removed and the resin composition was 47 vol%, and the inorganic filler was 28 vol. %, And a prepreg having a glass fiber substrate content of 25% by volume was obtained. Eight prepregs thus obtained were stacked, and 18 μm thick copper foil (3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.) was stacked on both upper and lower sides thereof. Heating and pressing were performed under the molding conditions of a temperature of 210 ° C. and a pressure of 3.0 MPa (30 kg / cm ² ) for 150 minutes to obtain a double-sided copper-clad laminate for a printed wiring board having a thickness of 0.8 mm. Next, using the obtained test piece from which the copper foil of the copper-clad laminate having a thickness of 0.8 mm was removed, the dielectric constant and dielectric loss tangent of 10 GHz were obtained by the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies). Was measured.

[Example 12]
In Example 12, instead of the base material used in Example 11, IPC No. A # 1037 E glass cloth was used to prepare a prepreg having a resin composition of 57% by volume, an inorganic filler of 33% by volume, and a glass fiber substrate of 10% by volume. In addition, the production method of the varnish of Example 12 was performed by the same method as Example 11. The method for producing the prepreg of Example 12 was performed in the same manner as in Example 1 except for the above points.

[Comparative Example 3]
As a comparative example of the above Examples 7 to 9, in Comparative Example 1, the varnish of Example 9 was used and IPC No. Using # 3313 E glass cloth, the varnish of Example 9 was impregnated and then heat-dried at a temperature of 170 ° C. for 5 minutes to remove the solvent, the resin composition was 52% by volume, and the inorganic filler was A prepreg of 15% by volume and 33% by volume of the glass fiber substrate was obtained. Eight prepregs thus obtained were stacked, and 18 μm thick copper foil (3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.) was stacked on both upper and lower sides thereof. Heating and pressing were performed under the molding conditions of a temperature of 210 ° C. and a pressure of 3.0 MPa (30 kg / cm ² ) for 150 minutes to obtain a double-sided copper-clad laminate for a printed wiring board having a thickness of 0.8 mm. Next, using the obtained test piece from which the copper foil of the copper-clad laminate having a thickness of 0.8 mm was removed, the dielectric constant and dielectric loss tangent of 10 GHz were obtained by the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies). Was measured.

[Comparative Example 4]
In Comparative Example 2, which is a comparative example of Examples 10 to 12, the varnish of Example 10 was used, and IPC No. After impregnating the varnish of Example 10 using # 3313 E glass cloth, it was dried by heating at a temperature of 170 ° C. for 5 minutes, the solvent was removed, the resin composition was 43% by volume, and the inorganic filler was A prepreg of 13% by volume and 44% by volume of the glass fiber substrate was obtained. Eight prepregs thus obtained were stacked, and 18 μm thick copper foil (3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.) was stacked on both upper and lower sides thereof. Temperature 210 ° C, pressure 3.0MP
a (30 kg / cm ² ), heated and pressed under molding conditions of 150 minutes, to obtain a double-sided copper-clad laminate for printed wiring board having a thickness of 0.8 mm. Next, using the obtained test piece from which the copper foil of the copper-clad laminate having a thickness of 0.8 mm was removed, the dielectric constant and dielectric loss tangent of 10 GHz were obtained by the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies). Was measured.

  FIG. 2 shows configurations and evaluation results of Examples 7 to 12 and Comparative Examples 3 and 4.

  As shown in FIG. 2, a resin composition having a dielectric constant (Dk) of 2.5 or more and 2.7 or less and a dielectric loss tangent (Df) of 0.005 or more and 0.007 or less, a glass fiber substrate, An inorganic filler, and a glass fiber substrate based on a specific gravity of 5% by volume to 30% by volume, a resin composition of 45% by volume to 90% by volume, and an inorganic filler of 3% by volume to 35% by volume. In Examples 7 to 12, it was confirmed that smaller Dk values and Df values can be obtained as compared with Comparative Examples 3 and 4 deviating from the volume content.

  As described above, according to the prepregs according to Examples 1 to 12 of the present invention, the dielectric constant (Dk) is 2.5 or more and 2.7 or less and the dielectric loss tangent (Df) is 0.005 or more and 0.007. The glass fiber base material based on specific gravity is 5 volume% or more and 30 volume% or less, and the resin composition is 45 volume% or more and 90 volume% including the following resin composition, a glass fiber base material, and an inorganic filler. Hereinafter, low Dk and low Df are realizable because an inorganic filler is 3 volume% or more and 35 volume% or less.

  Note that the present invention is not limited to the above-described embodiment, and can be modified as appropriate without departing from the spirit of the present invention.

Claims (4)

Including a resin composition having a dielectric constant (Dk) of 2.5 or more and 2.7 or less and a dielectric loss tangent (Df) of 0.005 or more and 0.007 or less, a glass fiber substrate, and an inorganic filler,
The glass fiber base based on specific gravity is 5 volume% or more and 30 volume% or less, the resin composition is 45 volume% or more and 90 volume% or less, and the inorganic filler is 3 volume% or more and 35 volume% or less. A prepreg.   The prepreg according to claim 1, wherein the inorganic filler includes silica. The resin composition is a polyphenylene ether resin composition represented by the following formula (I):
Including a polyphenylene ether crosslinkable curing agent,
The prepreg according to claim 1 or 2, wherein the number average molecular weight is 1000 to 7000.

[Wherein, X represents an aryl group, (Y) m represents a polyphenylene ether moiety, R ^{1 to} R ³ independently represent a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, and n represents 1 to 6 Q represents an integer of 1 to 4. ]   The resin composition includes an epoxy compound having a number average molecular weight of 1000 or less and not containing a halogen atom having at least two epoxy groups in one molecule, a polyphenylene ether having a number average molecular weight of 5000 or less, a cyanate ester compound, and the epoxy compound. The prepreg according to claim 1, further comprising: a curing catalyst that promotes a reaction between the polyphenylene ether and the cyanate ester compound that is a curing agent; and a halogen-based flame retardant.

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