JP6815792B2 - Thermosetting resin composition and prepreg using it, metal-clad laminate or printed wiring board - Google Patents

Description

The present invention uses the resin fine particles containing at least polyphenylene ether (PPE) and the resin composition containing the resin fine particles, the prepreg composed of the resin composition and the base material, and the prepreg, which are suitable as an electronic substrate material. The present invention relates to a laminated board or a printed wiring board for electric / electronic parts to be formed.

In recent years, due to remarkable progress in information network technology and expansion of services utilizing information networks, electronic devices are required to have a large amount of information and a high processing speed. In order to meet these demands, printed wiring board materials have low dielectric constant and low dielectric loss tangent in addition to the characteristics such as flame retardancy, heat resistance, and peel strength with copper foil, which have been conventionally required. Is required, and various attempts have been made to improve the resin composition.

Since PPE has a low dielectric constant and a dielectric loss tangent, it is suitable as a material for a printed wiring board that can meet the above requirements. On the other hand, PPE lacks solubility in organic solvents. Therefore, for example, Patent Document 1 describes a method for improving solubility by using a low molecular weight PPE whose number average molecular weight is adjusted to about 2000 when producing a prepreg necessary for producing a printed wiring board. There is. However, such a low molecular weight PPE does not necessarily achieve a sufficient low dielectric constant and low dielectric loss tangent because the proportion of phenolic hydroxyl groups in its structure increases as the molecular weight decreases. There wasn't.

As a method for solving such a problem, as described in Patent Document 2, there is a method in which PPE is pulverized by a method such as pulverization and dispersed as fine particles in an epoxy resin or the like. However, PPE that has not been reduced in molecular weight has low reactivity with an epoxy resin or the like, and in the case of an epoxy resin having poor compatibility with PPE, the adhesion between the epoxy resin and the PPE fine particles is weak in this method. In the heating process after molding the substrate, such as solder reflow, there is a risk that the resin layer may break due to the outgas component.

Japanese Patent No. 5793641 Special Table 2015-52087

Under the above circumstances, the problem to be solved by the present invention is that when the thermosetting resin composition is cured, the adhesiveness (for example, the peeling strength between layers in a multilayer board, or the curing of the thermosetting resin composition) A thermosetting resin composition that imparts the low dielectric constant and dielectric loss tangent inherent in PPE and excellent solder heat resistance to a cured product without impairing the peeling strength between the product and a metal foil such as copper foil. It is an object of the present invention to provide a prepreg composed of a sex resin composition and a base material, and a laminated board or a printed wiring board manufactured by using the prepreg.

As a result of diligent studies and experiments to solve the above problems, the present inventors consist of resin fine particles surface-treated with a metal alkoxide having a carbon-carbon unsaturated double bond group and a thermosetting resin, which will be described later. We have found that when a thermosetting resin composition is cured, the dielectric constant and dielectric loss tangent of the cured product can be reduced and excellent solder heat resistance can be achieved without impairing the adhesiveness with the copper foil. It came to be completed.
That is, the present invention is as follows.
[1]
A thermosetting resin composition composed of resin fine particles composed of at least one kind of resin containing polyphenylene ether (PPE) and a thermosetting resin.
The resin fine particles have the following formula:
{In the formula, R ¹ , R ² and R ³ each independently represent an alkyl group or hydrogen having 1 to 3 carbon atoms, and Z represents an arylene group or a carbonyl group}.
It is surface-treated with a metal alkoxide having a carbon-carbon unsaturated double bond group having the structure shown in.
The treatment amount of the metal alkoxide is 0.5 parts by mass to 5 parts by mass with respect to 100 parts by mass of the resin fine particles, and the resin fine particles are dispersed as particles in the thermosetting resin after curing. ing,
The thermosetting resin composition.
[2]
The thermosetting resin composition according to [1], wherein the metal alkoxide is a silane coupling agent.
[3]
The silane coupling agent has the following formula:
{In the formula, a is a natural number 1 to 3, b is a natural number 0 to 2, and R ₄ and R ₅ are independently alkyl groups or branched alkyl groups having 1 to 4 carbon atoms. And R ₆ represents an alkylene group having 1 to 12 carbon atoms or a branched alkylene group}
The thermosetting resin composition according to [2], which is at least one kind of silane coupling agent having the structure of.
[4]
The thermosetting resin composition according to [2] or [3], wherein the treated amount of the silane coupling agent in the resin fine particles is 1 part by mass to 4 parts by mass with respect to 100 parts by mass of the resin fine particles. ..
[5]
The thermosetting resin composition according to any one of [1] to [4], wherein the thermosetting resin is an epoxy resin.
[6]
The thermosetting resin composition according to any one of [1] to [5], wherein the resin fine particles have an average particle size of 10 μm or less and a maximum particle size of 30 μm or less.
[7]
The thermosetting resin composition according to any one of [1] to [6], wherein the PPE has a number average molecular weight of 8,000 to 30,000.
[8]
The item according to any one of [1] to [7], wherein the content of the resin fine particles is 5 parts by mass to 25 parts by mass with respect to 100 parts by mass in total of the resin fine particles and the thermosetting resin. Thermosetting resin composition.
[9]
A prepreg comprising the thermosetting resin composition according to any one of [1] to [8] and a base material.
[10]
A metal-clad laminate formed of the thermosetting resin composition according to any one of [1] to [8], the prepreg according to [9], and a metal foil.
[11]
A printed wiring board in which a part of the metal foil is removed from the metal-clad laminate according to [10].

According to the present invention, when cured, the PPE does not impair the adhesiveness (for example, the peeling strength between layers in a multilayer board, or the peeling strength between a cured product of a curable resin composition and a metal foil such as a copper foil). Manufactured using the thermosetting resin composition, the prepreg composed of the thermosetting resin composition and the base material, and the prepreg, which imparts the inherently low dielectric constant, dielectric positive contact and excellent solder heat resistance to the cured product. A laminated board or a printed wiring board can be obtained.

FIG. 1A is an SEM image of the resin fine particles A surface-treated in Example 1, and FIG. 1B is an EDX chart of the surface-treated resin fine particles A. FIG. 2 (a) is an SEM image of PPE without surface treatment, and FIG. 2 (b) is an EDX chart of PPE without surface treatment. FIG. 3 is an SEM image of a laminated board produced from the prepreg A obtained in Example 1. FIG. 4 is an SEM image of a laminated board produced from the prepreg O obtained in Comparative Example 1.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not intended to be limited to these aspects.

One aspect of the present invention is a thermosetting resin composition, and the thermosetting resin composition includes resin fine particles surface-treated with a metal alkoxide and a thermosetting resin.

The resin fine particles are composed of one or more kinds of resins containing at least PPE. When the resin fine particles are composed of a plurality of resins including PPE, the respective resins may be uniformly compatible or mixed, and the PPE covers the surface of the fine particles composed of other resins. You may be doing.

The resin fine particles preferably contain 25 parts by mass to 100 parts by mass of PPE, and more preferably 50 parts by mass to 100 parts by mass, based on 100 parts by mass of the resin fine particles before being treated with the metal alkoxide. By containing 25 parts by mass or more of PPE, the resin fine particles can impart characteristics such as low dielectric constant of PPE to the cured product when it is added to a thermosetting resin and cured.

The PPE contained in the resin fine particles is preferably the following general formula (1):
{In the formula, R1, R2, R3 and R4 each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. Represents an aryl group which may have a substituent, an amino group which may have a substituent, a nitro group or a carboxyl group}
Includes repeating structural units represented by.

Specific examples of PPE include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl-6). −Phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), etc., as well as 2,6-dimethylphenol and other phenols (eg, 2,3,6- Examples thereof include a copolymer with trimethylphenol, 2-methyl-6-butylphenol, etc., and a polyphenylene ether copolymer obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols. A preferred example is poly (2,6-dimethyl-1,4-phenylene ether).

In the specification of the present application, PPE means a polymer composed of a substituted or unsubstituted phenylene ether unit structure, but may contain other copolymerization components as long as the effects of the present invention are not impaired.

The number average molecular weight of PPE contained in the resin fine particles is preferably 5,000 or more and 100,000 or less, and more preferably 8,000 or more and 30,000 or less. When the number average molecular weight of PPE is 5,000 or more, the water absorption resistance, solder heat resistance, and adhesiveness (for example, peel strength or curability between layers of a multilayer board) of a cured product, which are desired in a printed wiring board or the like, are desired. It is preferable in that it gives good peel strength between the cured product of the resin composition and the copper foil or the like. Further, it is preferable that the number average molecular weight of PPE is 100,000 or less because good processability can be obtained when PPE is made into fine particles by a method such as pulverization.

Here, the number average molecular weight of PPE contained in the resin fine particles is standardized from the relational expression between the molecular weight and the elution time of the standard polystyrene sample measured under the same conditions by performing gel permeation chromatography (GPC) measurement by the method described later. The value measured in terms of polystyrene is taken as the number average molecular weight of PPE contained in the resin fine particles.

The average number of phenolic hydroxyl groups per molecule of PPE contained in the resin fine particles is the water absorption of a composite (for example, a laminated board) containing a cured product and a base material obtained by curing the thermosetting resin composition according to the present invention. From the viewpoint of suppressing the increase in the amount of the composite, and from the viewpoint of suppressing the increase in the dielectric constant and the dielectric loss tangent of the composite, the number is preferably 2.0 or less, more preferably 1.85 or less, still more preferably. It is 1.6 or less.

The average number of phenolic hydroxyl groups per molecule of PPE is defined as a value obtained by the following method. Polymer Papers, vol. 51, No. 7 (1994), in accordance with the method described on page 480, a dried product (PPE) of resin fine particles prepared for the measurement of the GPC was developed in a methylene chloride solution instead of chloroform, and tetramethylammonium hydroxide was used. The number of hydroxyl groups is determined from the value measured by an ultraviolet / visible absorptiometer for the change in absorbance of the sample obtained by adding the solution at a wavelength of 318 nm. Separately, the number average molecular weight of PPE is determined by GPC, and the number of molecules of PPE is determined using this value. From these values, the following formula:
The average number of hydroxyl groups per PPE molecule is calculated according to the average number of phenolic hydroxyl groups per molecule = number of hydroxyl groups / number of average molecules.

The average number of phenolic hydroxyl groups per PPE molecule is, for example, a mixture of PPE in which the phenolic hydroxyl group at the molecular terminal remains and PPE in which the phenolic hydroxyl group at the molecular terminal is modified with another functional group, and the like. It can be adjusted by changing the mixing ratio, or by changing the degree of substitution with other functional groups of the phenolic hydroxyl group at the molecular terminal. The mode of the above functional group is not particularly limited, and may be a benzyl group, an allyl group, a propagil group, a glycidyl group, a vinylbenzyl group, a methacryl group and the like.

Further, the PPE contained in the resin fine particles can be a reaction product of the PPE and an unsaturated carboxylic acid or an acid anhydride. Examples of unsaturated carboxylic acids or acid anhydrides include acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, glutaconic anhydride, citraconic anhydride and the like. The reaction is carried out by heating the PPE with an unsaturated carboxylic acid or acid anhydride in a temperature range of 100 ° C to 390 ° C. At this time, a radical initiator may coexist. Although both the solution method and the melt-mixing method can be used, the melt-mixing method using an extruder or the like can be performed more easily and is suitable for the object of the present invention. The ratio of unsaturated carboxylic acid or acid anhydride is 0.01 parts by weight or more and 5.0 parts by weight or less, preferably 0.1 parts by weight or more and 3.0 parts by weight or less with respect to 100 parts by weight of PPE.

As the resin other than PPE, a thermoplastic resin is preferable, and a thermoplastic resin that can be alloyed with PPE is more preferable. As an example, vinyl such as ethylene, propylene, butadiene, isoprene, styrene, divinylbenzene, methacrylic acid, acrylic acid, methacrylic acid ester, acrylic acid ester, vinyl chloride, acrylonitrile, maleic anhydride, vinyl acetate, and ethylene tetrafluoride. Examples thereof include homopolymers of compounds, copolymers of two or more kinds of vinyl compounds, polyamides, polyimides, polycarbonates, polyesters, polyacetals, polyphenylene sulfides, polyethylene glycols and the like.

The resin fine particles have an average particle size of 10 μm from the viewpoint of being able to more uniformly disperse the stress due to the thermal change when a rapid thermal change is applied to the cured product of the thermosetting resin such as a solder heat resistance test. It is preferable that the maximum particle size is 30 μm or less. By using resin fine particles having an average particle size of 10 μm or less, excellent adhesiveness (for example, peel strength between layers in a multilayer plate or peel strength between a cured product of a thermosetting resin composition and a copper foil or the like) is ensured. Not only that, it is also possible to give a more uniform dielectric constant and dielectric loss tangent to the entire cured product.

Further, it is preferable that the resin fine particles are uniformly dispersed in the thermosetting resin after curing. If the uneven distribution of the resin fine particles in the thermosetting resin after curing is remarkable, the cured product may be destroyed starting from the uneven distribution portion. Further, as a method of confirming the dispersed state of the resin fine particles in the thermosetting resin, a method of confirming the cross section of the thermosetting resin composition after curing with a scanning electron microscope (hereinafter referred to as “SEM”) or the like. Can be mentioned.

As an example of the method for measuring the particle size of the resin fine particles, a wet laser diffraction type particle size measuring device described later can be used. When measuring using the wet laser diffraction type particle size measuring device, water in which octylphenol ethoxylate typified by Triton X-100 (manufactured by Dow Chemical Co., Ltd.) is dissolved is added to a small amount of resin fine particles. , A measurement sample is prepared by dispersing by ultrasonic treatment or the like, and measurement is performed with the measuring device using water as a dispersion medium.

In order to obtain the resin fine particles having the above-mentioned particle size, it is preferable to process the resin raw material into fine particles before treating with the metal alkoxide. As a processing method, coarse resin particles are processed by applying energy to the resin particles, such as dry pulverization and wet pulverization; the resin is dissolved in a heated solvent and then cooled at a constant speed. A method for recrystallization; a method in which a resin solution is dispersed in water containing a surfactant to form an emulsion, and then gently heated to remove the solvent to form particles. Dry pulverization is desirable from the viewpoint of cost or productivity. Examples of dry pulverization include jet mills, ball mills, turbo mills and the like. Further, in order to obtain fine particles having a desired particle size, coarse or fine particles may be removed by classifying with a sieve or the like after processing from the raw material particles.

The resin fine particles are surface-treated with the metal alkoxide, and are treated with 0.5 parts by mass to 5 parts by mass of the metal alkoxide with respect to 100 parts by mass of the resin fine particles not surface-treated. It is more preferable that the treatment is carried out in an amount of 1 part by mass to 4 parts by mass. By surface-treating with a metal alkoxide by the method described later, good solder heat resistance can be imparted to the cured product of the thermosetting resin composition according to the present invention. Although the principle of imparting good solder heat resistance is unknown, PPE having a specific number average molecular weight constituting the resin fine particles according to this embodiment has poor reactivity with a thermosetting resin such as an epoxy resin. However, as will be described later, the solder heat resistance of the cured product of the thermosetting resin composition according to this mode is improved by treating the metal alkoxide having a carbon-carbon unsaturated double bond group in a hydrolyzed state. Therefore, by the surface treatment, any one of the chemical bond formed by the condensation of metal alkoxides such as hydroxyl group and siloxane bond, the carbon-carbon unsaturated double bond group, or a combination thereof is exposed on the surface. It is presumed that the improvement in the wettability of the resin fine particles with respect to the thermosetting resin and the improvement in the dispersibility of the resin fine particles in the thermosetting resin contribute to the improvement.

The metal alkoxide has the following formula:
{In the formula, R ¹ , R ² and R ³ each independently represent an alkyl group or hydrogen having 1 to 3 carbon atoms, and Z represents an arylene group or a carbonyl group}.
Except for having a carbon-carbon unsaturated double bond group having the structure shown in (1), examples thereof include silicon alkoxide (hereinafter, “silane coupling agent”), titanium alkoxide, aluminum alkoxide, and zirconium alkoxide. And so on.

The metal alkoxide is preferably a silane coupling agent. Further, more preferably, the following formula:
{In the formula, a is a natural number 1 to 3, b is a natural number 0 to 2, and R ₄ and R ₅ are independently alkyl groups or branched alkyl groups having 1 to 4 carbon atoms. And R ₆ represents an alkylene group having 1 to 12 carbon atoms or a branched alkylene group}
It is a silane coupling agent having the structure shown in.

Examples of the silane coupling agent include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and γ-methacryloxy. Examples thereof include propyltris 2-propoxysilane and 8-methacryloxyoctyltrimethoxysilane.

When the surface treatment of the resin fine particles is performed with a metal alkoxide, it is preferable that the metal alkoxide is dissolved in water in advance and then the surface treatment is performed. The treatment method is not particularly limited, and examples thereof include a dry treatment method, a wet treatment method, and an integral blending method. The dry treatment method and the wet treatment method mainly include (1) preparing an aqueous solution of the compound, (2) mixing the resin fine particles not surface-treated with the aqueous solution, (3) drying the mixture, and (4). It is processed by the operation of crushing the resin fine particles aggregated by drying. The difference between the dry treatment method and the wet treatment method lies in the method of mixing the resin fine particles and the aqueous solution in the operation (2). In the dry treatment method, in the operation (2), a small amount of the aqueous solution is sprayed and mixed by a spray or the like while stirring the resin fine particles, for example. Further, in the wet treatment method, in the operation (2), resin fine particles are added to a large amount of the aqueous solution and dispersed in a slurry to be mixed. The dry treatment method is preferable from the viewpoint of achieving a more homogeneous treatment state with respect to the resin fine particles when drying in the operation (3).

Regarding the operation (1), the pH of the metal alkoxide may be adjusted with an acid or an alkali with respect to water from the viewpoint of enhancing the stability after hydrolysis. Further, from the viewpoint that the compound can be dissolved to prepare a homogeneous aqueous solution, and the wettability to the resin fine particles that have not been surface-treated can be improved to achieve a homogeneous treated state, it can be mixed with water such as methanol. An organic solvent may be added.

Regarding the operation (2), when performing a dry treatment, it is more homogeneous to perform an operation such as making the mist diameter of the aqueous solution to be sprayed finer and sufficiently stirring using a Henschel mixer or the like. It is preferable from the viewpoint that the state can be imparted to the resin fine particles.

Regarding the operation (3), the drying method is not particularly limited, but it is preferable to appropriately control the drying temperature or the drying time and sufficiently remove water and an organic solvent.

Regarding the operation (4), when the resin fine particles are aggregated, it is preferable to crush them to the same particle size as before the aggregation by an appropriate method. Although not particularly limited, a jet mill, a ball mill, a turbo mill, or the like can be used as an example.

The thermosetting resin composition used in the present embodiment contains the resin fine particles and a thermosetting resin. The thermosetting resin is not particularly limited, but is limited to epoxy resin, polyimide resin, bismaleimide triazine resin, phenol resin, bismaleimides, cyanate esters, polybutadiene or similar compounds, and triallyl isocyanurate and styrene. , Vinyl compounds typified by divinylbenzene and the like can be mentioned as an example. The resins may be used alone or in combination of two or more.

The thermosetting resin is preferably an epoxy resin. Although not particularly limited, examples of epoxy resins include alicyclic epoxy compounds, bisphenol A type epoxy compounds, bisphenol A novolac type epoxy compounds, bisphenol F type epoxy compounds, bisphenol F novolac type epoxy compounds, phenol novolac type epoxy compounds, and cresol novolac. Examples thereof include type epoxy compounds, naphthalene type epoxy compounds, and biphenyl type epoxy compounds. These may be used alone or in combination of two or more.
The epoxy resin preferably contains a curing agent. Examples of the curing agent include, but are not limited to, aliphatic polyamines, polyaminoamides, polymercaptans, aromatic polyamines, acid anhydrides, phenol novolac compounds, dicyandiamides, cyanate ester compounds and the like. These may be used alone or in combination of two or more.
The epoxy resin can contain a curing accelerator. Although not particularly limited, examples of the curing accelerator include tertiary amine compounds, tertiary amine compound salts, imidazole compounds, phosphine compounds, phosphonium compound salts and the like. These may be used alone or in combination of two or more.

The content of the resin fine particles in the thermosetting resin composition is preferably 5 parts by mass to 25 parts by mass, and more preferably 7 to 20 parts by mass with respect to 100 parts by mass in total with the thermosetting resin. .. When the thermosetting resin composition contains 5 parts by mass or more of the resin fine particles, the effect of reducing the dielectric constant or the dielectric loss tangent can be imparted to the resin composition, and the content of the resin fine particles is 25 parts by mass or less. As a result, excellent solder heat resistance can be imparted without impairing the adhesiveness (for example, the peeling strength between layers in a multilayer plate or the peeling strength between a cured product of a curable resin composition and a metal foil such as a copper foil). ..

In the present embodiment, in addition to the resin fine particles and the thermosetting resin, the thermosetting resin composition is added, for example, a reaction initiator or reaction accelerator of the thermosetting resin, a flame retardant, a silica filler, and the like. Agents and the like can be preferably blended in a manner similar to these aspects known in the art. Such formulations are also included in the present disclosure. Further, the thermosetting resin composition according to the present embodiment can be preferably used to form a varnish, a prepreg, a metal-clad laminate, and a printed wiring board.

The thermosetting resin composition according to the present embodiment may further contain an appropriate additive depending on the purpose. Examples of the additive include a heat stabilizer, an antioxidant, a UV absorber, a surfactant, a lubricant, a filler, a polymer additive and the like.

Another aspect of the present invention provides a prepreg composed of the thermosetting resin composition and a base material. For example, a prepreg can be produced by impregnating a base material such as glass cloth with a thermosetting resin, a solvent thereof, and a varnish containing the resin fine particles, and then drying and removing the solvent component with a hot air dryer or the like. ..

As the base material, various glass cloths such as roving cloth, cloth, chopped mat, and surface mat; asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloth; all aromatic polyamide fibers, all aromatic polyesters. Woven or non-woven fabrics obtained from liquid crystal fibers such as fibers and polybenzoxazole fibers; natural fiber fabrics such as cotton cloth, linen cloth and felt; carbon fiber cloth, kraft paper, cotton paper, cloth obtained from paper-glass mixed fiber yarn, etc. Natural cellulose-based base material; polytetrafluoroethylene porous film; etc. can be used alone or in combination of two or more.

The ratio of the thermosetting resin composition to the prepreg is preferably 30 parts by mass to 80 parts by mass, and more preferably 40 parts by mass to 70 parts by mass with respect to 100 parts by mass of the total amount of the prepreg. When the above ratio is 30 parts by mass or more, excellent insulation reliability is obtained when the prepreg is used for forming an electronic substrate, for example, and when it is 80 parts by mass or less, for example, the obtained electronic substrate is bent. Excellent mechanical properties such as elastic modulus.

In another aspect of the present invention, a metal-clad laminate in which a cured product composite containing a cured product of the thermosetting resin composition and a base material and a metal foil are laminated can be formed. The laminated board is preferably one in which the cured product composite and the metal foil are overlapped and adhered to each other, and is preferably used as a material for an electronic substrate. As the metal foil, for example, aluminum foil and copper foil can be used, and among them, copper foil is preferable because it has low electrical resistance. The cured product composite to be combined with the metal foil may be one or more, and the metal foil is laminated on one side or both sides of the composite depending on the application and processed into a laminated plate. As a method for producing a laminated board, for example, a composite composed of a thermosetting resin composition and a base material (for example, the above-mentioned prepreg) is formed, and after laminating this with a metal foil, a thermosetting resin is produced. Examples thereof include a method of obtaining a laminated plate in which a cured product laminate and a metal foil are laminated by curing the composition. One of the particularly preferable uses of the laminated board is a printed wiring board. The printed wiring board preferably has at least a part of the metal foil removed from the metal-clad laminate.

Another aspect of the present invention provides a printed wiring board containing a cured product of the thermosetting resin composition and a base material. The printed wiring board of the present invention can typically be formed by a method of pressure heating molding using the prepreg of the present invention described above. Examples of the base material include the same materials as those described above for the prepreg. Since the printed wiring board of the present invention is formed by using the thermosetting resin composition, it can have excellent insulation reliability and mechanical properties.

Hereinafter, the present embodiment will be specifically described with reference to Examples, but the present embodiment is not limited to the following Examples.

The physical characteristics described in the following Examples, Comparative Examples, and Test Examples were measured or observed by the following methods.

(1) Number average molecular weight of PPE Using GPC analysis, the number average molecular weight was determined by comparison with the elution time of standard polystyrene having a known molecular weight.
After preparing a measurement sample with a sample concentration of 0.2 w / vol% (solvent: chloroform), use HLC-8220 GPC (manufactured by Toso Co., Ltd.) as the measuring device, and column: Shodex GPC KF-405L HQ x 3 (Showa Denko Co., Ltd.) Measurement was performed under the conditions of (manufactured by the company), eluent: chloroform, injection volume: 20 μL, flow rate: 0.3 mL / min, column temperature: 40 ° C., detector: RI.

(2) Dielectric constant and dielectric loss tangent of the laminated plate The dielectric constant and dielectric loss tangent of the laminated plate at 1 GHz were measured by the cavity resonance method.
A network analyzer (N5230A, manufactured by Agilent Technologies) and a cavity resonator (Cavity Resonator CP series) manufactured by Kanto Electronics Applied Development Co., Ltd. were used as measuring devices.
The laminated board is cut into a size of about 2 mm in width and 90 mm in length, placed in an oven at 105 ° C. ± 2 ° C. and dried for 2 hours, and then dried in an environment at 23 ° C. and a relative humidity of 65 ± 5% for 96 ± 5 hours. Using the test piece prepared by placing it, the dielectric constant and the dielectric loss tangent were measured using the above measuring device in an environment of 23 ° C. and a relative humidity of 65 ± 5%.

(3) Water absorption rate of the laminated board The laminated board was subjected to a water absorption acceleration test, and the water absorption rate was determined from the increased mass.
A test piece was prepared by cutting a laminated board into a 50 mm square. After drying the test piece at 105 ° C. for 60 minutes, the mass was measured and used as the mass (g) before the accelerated test. Next, the mass after performing the accelerated test under the conditions of temperature: 121 ° C., pressure: 2 atm, and time: 4 hours was measured and used as the mass (g) after the accelerated test.
Using the mass (g) before the accelerated test and the mass (g) after the accelerated test, the following formula:
Water absorption (mass%) = (mass before accelerated test-mass after accelerated test) / mass before accelerated test x 100
The water absorption rate was calculated by the above method, and the average value of the measured values of the four test pieces was obtained.

(4) Solder Heat Resistance After Water Absorption Test of Laminated Plate A solder heat resistance test at 288 ° C. was performed using the laminated plate after measuring the water absorption rate described in (3) above. The laminated board after the water absorption acceleration test was immersed in a solder bath at 288 ° C. for 20 seconds and visually observed. Laminated plates in which no swelling, peeling, or whitening was confirmed even when immersed in a solder bath were evaluated as "○ (good)". In addition, the laminated board generated in any part of swelling, peeling, and whitening due to immersion in the solder bath was evaluated as "Δ (allowable)", and when it occurred on the entire surface, the laminated board was evaluated as "x (defective)".

(5) Copper foil peeling strength of laminated board (peeling strength N / mm)
The stress when the copper foil of the copper-clad laminate was peeled off at a constant speed was measured. A copper-clad laminate using a 35 μm thick copper foil (GTS-MP foil, manufactured by Furukawa Denki Kogyo Co., Ltd.) produced by the method described later was cut into a size of 15 mm in width × 150 mm in length, and an autograph (AG-) was cut out. Using 5000D, manufactured by Shimadzu Corporation), measure the average value of the load when the copper foil is peeled off at an angle of 90 ° C. at a speed of 50 mm / min, and measure the average value of the five measurements. I asked.

(6) Measurement of particle size of resin fine particles Using a laser diffraction type particle size measuring device (Microtrac MT3000-II manufactured by Microtrac Bell Co., Ltd.), the average particle size and the maximum particle size of the resin fine particles before and after the treatment were measured. Based on the data obtained by the operation described later, the particle size having a 50% particle volume distribution (d50) is the average particle size, and the particle size having a 100% particle volume distribution (d100), with the smaller particle size as 0. Was taken as the maximum particle size.
(Operation of particle size measurement)
10 μg of resin fine particles, 10 ml of a 0.2 wt% sodium hexametaphosphate aqueous solution, and several drops of a 10 wt% Triton X-100 aqueous solution were added to the screw tube, and the mixture was sufficiently dispersed by an sonicator to prepare a sample for measurement. Using this measurement sample, in the measuring device using water as a dispersion medium, measurement conditions: transmission, particle refractive index: 1.60, particle shape: non-spherical, solvent (dispersion medium) refractive index: 1. The condition was set to 33, and the particle size was measured.

(7) Observation of cross section of laminated board by SEM The cross section of the laminated board was observed using SEM (S-4100, manufactured by Hitachi High-Technologies Corporation). After cutting the sample for observation into 10 mm squares, it is embedded in a resin mixed with 90 parts by mass of Epomount main agent (manufactured by Refine Tech Co., Ltd.) and 10 parts by mass of Epomount curing agent (manufactured by Refine Tech Co., Ltd.) at room temperature. After allowing to stand for 1 day, the embedded material was cut and polished so that the cross section of the sample could be observed, and then a sputtering apparatus (E-1020, manufactured by Hitachi, Ltd.) using gold-palladium as a target was used. The cross section was subjected to a conductive treatment to prepare the product. At the time of observation, the acceleration voltage was set to 20 kV for observation.

(8) Analysis of resin fine particles by EDX The resin fine particles before and after the treatment are analyzed by an energy dispersive X-ray analyzer (hereinafter referred to as "EDX") (EMAX ENERGY EX-250, manufactured by HORIBA, Ltd.) attached to the SEM. did. The measurement sample was prepared by fixing the resin fine particles on a conductive tape attached to a measurement sample table and then subjecting the sputtering apparatus using gold-palladium as a target to a conductive treatment. At the time of observation, the acceleration voltage was set to 20 kV and the measurement was performed.

<Example 1>
1.0 part by mass of acetic acid was added to 268 parts by mass of deionized water to dissolve it. A solution prepared by dissolving 23.8 parts by mass of 3-methacryloxypropyltrimethoxysilane in an equal amount of methanol was slowly added dropwise to the obtained aqueous solution while stirring the aqueous solution. After continuing stirring for 3 hours, 244.6 parts by mass of methanol was added to prepare a treatment liquid A.

100 parts by mass of PPE (S202A, manufactured by Asahi Kasei Co., Ltd., number average molecular weight 19,900, average number of phenolic hydroxyl groups per molecule 1.93) pulverized in advance to an average particle size of 4 μm and a maximum particle size of 11 μm by a jet mill. Was added to the SUS container. Put the treatment liquid A in a hand spray, and while stirring the PPE, add 47.4 parts by mass of the treatment liquid A so that the treatment amount of 3-methacryloxypropyltrimethoxysilane is 2 parts by mass with respect to 100 parts by mass of PPE. It was sprayed into a SUS container. Then, after air-drying for 1 day, it was dried for 8 hours in a dryer set at 100 ° C. A sample in which particles were agglomerated by drying was crushed using a mortar to obtain resin fine particles A (average particle size 4 μm, maximum particle size 13 μm).

When the prepreg was prepared, the bisphenol A novolak type epoxy was placed in a SUS container so that the content of the resin fine particles in the thermocurable resin composition was 15 parts by mass with respect to 100 parts by mass in total with the thermocurable resin. Resin (157S70B75, manufactured by Mitsubishi Chemical Corporation, containing 25% by mass of MEK) 39.8 parts by mass, brominated bisphenol A type epoxy resin (5050T60, manufactured by Mitsubishi Chemical Corporation, containing 40% by mass of toluene) 40.8 mass 7.3 parts by mass of bisphenol A type epoxy resin (1001B80, manufactured by Mitsubishi Chemical Co., Ltd., containing 20% by mass of MEK), bisphenol A novolac type resin (YLH129B65H, manufactured by Mitsubishi Chemical Co., Ltd., containing 35% by mass of MEK) 38.0 parts by mass, 0.4 parts by mass of 2-methoxyethanol solution of 2-ethyl-4-methylimidazole (Shikoku Kasei Co., Ltd.) (containing 50% by mass of 2-methoxyethanol), 34.1 parts by mass of MEK, And 15 parts by mass of the resin fine particles A were added. A varnish A for coating was obtained by performing dispersion treatment with a homogenizer (HM-300, manufactured by HSIANGTAI MACHINERY INDUSTRY) at 8000 rpm for 10 minutes so that the whole was uniform.

The coating varnish A is impregnated into a 0.1 mm thick E glass glass cloth (2116 style, manufactured by Asahi Schebel), excess varnish is scraped off with a slit, and then the solvent is dried and removed at 160 ° C. , A prepreg A having a resin content of 56% by mass was obtained.

<Example 2>
Resin fine particles B (average particle size 4 μm, maximum particle size 13 μm) were obtained by the same method as in Example 1 except that 3-methacryloxypropyltrimethoxysilane was changed to 8-methacryloxyoctyltrimethoxysilane. Further, a coating varnish B was obtained by the same method as in Example 1 except that the resin fine particles A were changed to the resin fine particles B, and a prepreg B having a resin content of 56% by mass was obtained.

<Example 3>
Resin fine particles C (average particle size 4 μm, maximum particle size 13 μm) were obtained by the same method as in Example 1 except that 3-methacryloxypropyltrimethoxysilane was changed to 3-methacryloxypropylmethyldimethoxysilane. Further, a coating varnish C was obtained by the same method as in Example 1 except that the resin fine particles A were changed to the resin fine particles C, and a prepreg C having a resin content of 56% by mass was obtained.

<Example 4>
Resin fine particles D (average particle size 4 μm, maximum particle size 13 μm) were obtained by the same method as in Example 1 except that 3-methacryloxypropyltrimethoxysilane was changed to 3-methacryloxypropyltriethoxysilane. Further, a coating varnish D was obtained by the same method as in Example 1 except that the resin fine particles A were changed to the resin fine particles D, and a prepreg D having a resin content of 56% by mass was obtained.

<Example 5>
Resin fine particles E (average) by the same method as in Example 1 except that the amount of the treatment liquid is changed to 11.8 parts by mass so that the treatment amount of 3-methacryloxypropyltrimethoxysilane is 0.5 parts by mass. A particle size of 4 μm and a maximum particle size of 12 μm) were obtained. Further, a coating varnish E was obtained by the same method as in Example 1 except that the resin fine particles A were changed to the resin fine particles E, and a prepreg E having a resin content of 56% by mass was obtained.

<Example 6>
Resin fine particles F (average particle size) in the same manner as in Example 1 except that the amount of the treatment liquid was changed to 118.4 parts by mass so that the amount of 3-methacryloxypropyltrimethoxysilane treated was 5 parts by mass. 4 μm, maximum particle size 14 μm) was obtained. Further, a coating varnish F was obtained by the same method as in Example 1 except that the resin fine particles A were changed to the resin fine particles F, and a prepreg F having a resin content of 56% by mass was obtained.

<Example 7>
The amount of the treatment liquid was changed so that the particle size of the PPE used was changed to an average particle size of 9 μm and a maximum particle size of 26 μm, and the treatment amount of 3-methacryloxypropyltrimethoxysilane was 0.5 parts by mass. Resin fine particles G (average particle size 9 μm, maximum particle size 28 μm) were obtained by the same method as in Example 1 except for changing to 8 parts by mass. Further, a coating varnish G was obtained by the same method as in Example 1 except that the resin fine particles A were changed to the resin fine particles G, and a prepreg G having a resin content of 56% by mass was obtained.

<Example 8>
The particle size of the PPE used was changed to an average particle size of 9 μm and a maximum particle size of 26 μm, and the amount of the treatment liquid was increased to 118.4 parts by mass so that the amount of 3-methacryloxypropyltrimethoxysilane treated was 5 parts by mass. Resin fine particles H (average particle size 10 μm, maximum particle size 30 μm) were obtained by the same method as in Example 1 except for modification. Further, a coating varnish H was obtained by the same method as in Example 1 except that the resin fine particles A were changed to the resin fine particles H, and a prepreg H having a resin content of 56% by mass was obtained.

<Example 9>
When the prepreg was prepared, the amount of the resin fine particles A added was 4.5 so that the content of the resin fine particles in the thermosetting resin composition was 5 parts by mass with respect to 100 parts by mass in total with the thermosetting resin. A coating varnish I was obtained in the same manner as in Example 1 except that the amount of MEK added was changed to 26.4 parts by mass, and a prepreg I having a resin content of 56% by mass was obtained.

<Example 10>
When the prepreg was prepared, the amount of the resin fine particles A added was 28.3 so that the content of the resin fine particles in the thermosetting resin composition was 25 parts by mass with respect to 100 parts by mass in total with the thermosetting resin. A coating varnish J was obtained in the same manner as in Example 1 except that the amount of MEK added was changed to 44.2 parts by mass, and a prepreg J having a resin content of 56% by mass was obtained.

<Example 11>
Example 1 except that the PPE used is changed to S201A (manufactured by Asahi Kasei Co., Ltd., number average molecular weight 25,200, average number of phenolic hydroxyl groups per molecule is 1.99, average particle size 5 μm, maximum particle size 13 μm). Resin fine particles K (average particle size 5 μm, maximum particle size 15 μm) were obtained by the same method as above. Further, a coating varnish K was obtained by the same method as in Example 1 except that the resin fine particles A were changed to the resin fine particles K, and a prepreg K having a resin content of 56% by mass was obtained.

<Example 12>
Resin fine particles L (average particle size 4 μm, average particle size 4 μm, made by Asahi Kasei Co., Ltd., number average molecular weight 12,700, average particle size 4 μm, maximum particle size 11 μm) except that the PPE used is changed to S203A. Maximum particle size 13 μm) was obtained. Further, a coating varnish L was obtained by the same method as in Example 1 except that the resin fine particles A were changed to the resin fine particles L, and a prepreg L having a resin content of 56% by mass was obtained.

<Example 13>
Resin fine particles M (average particle size 4 μm, maximum particle size 13 μm) were obtained by the same method as in Example 1 except that 3-methacryloxypropyltrimethoxysilane was changed to 3-acryloxypropyltrimethoxysilane. Further, a coating varnish M was obtained by the same method as in Example 1 except that the resin fine particles A were changed to the resin fine particles M, and a prepreg M having a resin content of 56% by mass was obtained.

<Example 14>
Resin fine particles N (average particle size 4 μm, maximum particle size 13 μm) were obtained by the same method as in Example 1 except that 3-methacryloxypropyltrimethoxysilane was changed to p-styryltrimethoxysilane. Further, a coating varnish N was obtained by the same method as in Example 1 except that the resin fine particles A were changed to the resin fine particles N, and a prepreg N having a resin content of 56% by mass was obtained.

<Comparative example 1>
A coating varnish O was obtained by the same method as in Example 1 except that a coating varnish was obtained using PPE that had not been surface-treated with a silane coupling agent, and a prepreg O having a resin content of 56% by mass was obtained. Obtained.

<Comparative example 2>
Resin fine particles P (average particle size) in the same manner as in Example 1 except that the amount of the treatment liquid was changed to 142.1 parts by mass so that the amount of 3-methacryloxypropyltrimethoxysilane treated was 6 parts by mass. 5 μm, maximum particle size 14 μm) was obtained. Further, a coating varnish P was obtained by the same method as in Example 1 except that the resin fine particles A were changed to the resin fine particles P, and a prepreg P having a resin content of 56% by mass was obtained.

<Comparative example 3>
Resin fine particles Q (average particle size 4 μm, maximum particle size 13 μm) were obtained by the same method as in Example 1 except that 3-methacryloxypropyltrimethoxysilane was changed to 3-glycidoxypropyltrimethoxysilane. Further, a coating varnish Q was obtained by the same method as in Example 1 except that the resin fine particles A were changed to the resin fine particles Q, and a prepreg Q having a resin content of 56% by mass was obtained.

<Comparative example 4>
Resin fine particles R (average particle size 4 μm, maximum particle size 13 μm) were obtained by the same method as in Example 1 except that 3-methacryloxypropyltrimethoxysilane was changed to 3-phenylaminopropyltrimethoxysilane. Further, a coating varnish R was obtained by the same method as in Example 1 except that the resin fine particles A were changed to the resin fine particles R, and a prepreg R having a resin content of 56% by mass was obtained.

<Comparative example 5>
Resin fine particles S (average particle size 4 μm, maximum particle size 13 μm) were obtained by the same method as in Example 1 except that 3-methacryloxypropyltrimethoxysilane was changed to allyltrimethoxysilane. Further, a coating varnish S was obtained by the same method as in Example 1 except that the resin fine particles A were changed to the resin fine particles S, and a prepreg S having a resin content of 56% by mass was obtained.

<Comparative Example 6>
Resin fine particles T (average particle size 4 μm, maximum particle size 13 μm) were obtained by the same method as in Example 1 except that 3-methacryloxypropyltrimethoxysilane was changed to 3-mercaptopropyltrimethoxysilane. Further, a coating varnish T was obtained by the same method as in Example 1 except that the resin fine particles A were changed to the resin fine particles T, and a prepreg T having a resin content of 56% by mass was obtained.

<Comparative Example 7>
A coating varnish U was obtained in the same manner as in Example 1 except that the amount of MEK added was changed to 15.3 parts by mass without adding resin fine particles, and a prepreg U having a resin content of 56% by mass was obtained. Obtained.

<Test example>
Substrate samples were prepared using the prepregs A to U obtained in Examples 1 to 14 and Comparative Examples 1 to 7, and the electrical characteristics (dielectric constant, dielectric loss tangent), water absorption coefficient, and solder heat resistance after water absorption were prepared. , Copper foil peeling strength was compared and evaluated.

A sample for measuring the dielectric constant and the dielectric loss tangent and a sample for observing the cross section of the laminated plate were prepared by the following methods. Eight prepregs obtained in Examples or Comparative Examples are stacked and vacuum pressed under the condition of a pressure of 5 kg / cm ² while heating from room temperature at a heating rate of 2.5 ° C./min, and the temperature rises when the temperature reaches 130 ° C. Vacuum press under the condition of pressure 30 kg / cm ² while heating at a speed of 5 ° C / min, and when the temperature reaches 195 ° C, vacuum press under the condition of pressure 30 kg / cm ² and time 60 minutes while keeping the temperature at 195 ° C. A laminated board was produced by performing the above. The laminated plate was cut into 100 mm squares and processed to the size of the above-mentioned test piece, and then used as a sample for measuring the dielectric constant and the dielectric loss tangent and a sample for cross-section observation.

A sample for evaluating the water absorption rate and the solder heat resistance after the water absorption test was prepared by the following method. Two prepregs obtained in Examples or Comparative Examples were stacked, and a copper foil (GTS foil, manufactured by Furukawa Denki Kogyo Co., Ltd.) with a thickness of 12 μm was laminated on top of and below the prepreg, and the temperature was raised from room temperature to 2.5 ° C. Vacuum press under the condition of pressure 5 kg / cm ² while heating in minutes, and when reaching 130 ° C, perform vacuum press under the condition of pressure 30 kg / cm ² while heating at a heating rate of 5 ° C / min, 195. When the temperature reached ℃, a double-sided copper-clad laminate was obtained by vacuum pressing under the conditions of a pressure of 30 kg / cm ² and a time of 60 minutes while maintaining the temperature at 195 ° C. Next, the copper-clad laminate was cut into 100 mm squares, the copper foil was removed by etching, processed to the size of the above-mentioned test piece, and then a sample for evaluating the water absorption rate and the solder heat resistance after the water absorption test was obtained. It was.

A sample for measuring the peel strength of copper foil was prepared by the following method. Two prepregs obtained in Examples or Comparative Examples were laminated, and a copper foil (GTS-MP foil, manufactured by Furukawa Denki Kogyo Co., Ltd.) having a thickness of 35 μm was laminated on the top and bottom thereof, and the temperature was raised from room temperature to 2.5. Vacuum press under the condition of pressure 5 kg / cm ² while heating at ° C / min, and when reaching 130 ° C, perform vacuum press under the condition of pressure 30 kg / cm ² while heating at the heating rate of 5 ° C / min. When the temperature reached 195 ° C., a double-sided copper-clad laminate was produced by vacuum pressing under the conditions of a pressure of 30 kg / cm ² and a time of 60 minutes while maintaining the temperature at 195 ° C. This double-sided copper-clad laminate was processed to the size of the above-mentioned test piece, and then used as a sample for measuring the copper foil peeling strength.

The dielectric constant, dielectric loss tangent, water absorption, solder heat resistance after water absorption, and copper foil peeling strength were measured using the above-mentioned laminated plate or double-sided copper-clad laminate. The results are shown in Tables 1 and 2 below.

The resin fine particles A and PPE without surface treatment were analyzed by EDX. SEM images and EDX charts of the resin fine particles A and the PPE without surface treatment are shown in FIGS. 1 and 2, respectively.
(Comparison between FIGS. 1 and 2)
Comparing the two samples, it was possible to confirm the signal of silicon derived from 3-methacryloxypropyltrimethoxysilane only from the resin fine particles A.

Further, using the prepreg A and the prepreg O, the cross section of the sample prepared for the above-mentioned measurement of the dielectric constant and the dielectric loss tangent was photographed by SEM. Cross-sectional SEM images of the sample prepared from prepreg A and the sample prepared from prepreg O are shown in FIGS. 3 and 4, respectively.
(Comparison between FIGS. 3 and 4)
Comparing the two samples, it was confirmed that in the sample prepared from prepreg A, the resin fine particles were uniformly dispersed in the epoxy resin.

Claims (9)

A thermosetting resin composition composed of resin fine particles composed of at least one kind of resin containing polyphenylene ether (PPE) and a thermosetting resin.
The resin fine particles have the following formula:
{In the formula, R ¹ , R ² and R ³ each independently represent an alkyl group or hydrogen having 1 to 3 carbon atoms, and Z represents an arylene group or a carbonyl group}.
It is surface-treated with a metal alkoxide having a carbon-carbon unsaturated double bond group having the structure shown in.
The metal alkoxide is a silane coupling agent.
The amount of the metal alkoxide treated is 0.5 parts by mass to 5 parts by mass with respect to 100 parts by mass of the resin fine particles .
The resin fine particles are dispersed as particles in the thermosetting resin after curing , and
The thermosetting resin is an epoxy resin.
The thermosetting resin composition. The silane coupling agent has the following formula:
{In the formula, a is a natural number 1 to 3, b is a natural number 0 to 2, and R ₄ and R ₅ are independently alkyl groups or branched alkyl groups having 1 to 4 carbon atoms. And R ₆ represents an alkylene group having 1 to 12 carbon atoms or a branched alkylene group}
It is at least one or more of the silane coupling agent having the structure of, the thermosetting resin composition of claim 1. The thermosetting resin composition according to claim 1 or 2 , wherein the treated amount of the silane coupling agent in the resin fine particles is 1 part by mass to 4 parts by mass with respect to 100 parts by mass of the resin fine particles. The thermosetting resin composition according to any one of claims 1 to 3 , wherein the resin fine particles have an average particle size of 10 μm or less and a maximum particle size of 30 μm or less. The thermosetting resin composition according to any one of claims 1 to 4 , wherein the PPE has a number average molecular weight of 8,000 to 30,000. The thermosetting according to any one of claims 1 to 5 , wherein the content of the resin fine particles is 5 parts by mass to 25 parts by mass with respect to 100 parts by mass in total of the resin fine particles and the thermosetting resin. Sex resin composition. A prepreg comprising the thermosetting resin composition according to any one of claims 1 to 6 and a base material. A metal-clad laminate formed of the thermosetting resin composition according to any one of claims 1 to 6 or the prepreg according to claim 7 , and a metal foil. A printed wiring board in which a part of the metal foil is removed from the metal-clad laminate according to claim 8 .