JP2018035217A - Thermosetting resin composition, and prepreg, metal-clad laminate or printed wiring board using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which imparts low dielectric constant and dielectric tangent inherent to polyphenylene ether (PPE), and excellent solder heat resistance to a cured product without impairing adhesiveness when a thermosetting resin composition is cured; a prepreg formed of the thermosetting resin composition and a base material; and a laminated plate and a printed wiring board produced using the prepreg.SOLUTION: A thermosetting resin composition is formed of resin fine particles composed of at least one or more resins containing PPE and a thermosetting resin, where the resin fine particles are surface-treated with metal alkoxide having a carbon-carbon unsaturated double bond group, a treatment amount of the metal alkoxide is 0.5-5 pts.mass with respect to 100 pts.mass of the resin fine particles, and the resin fine particles are dispersed in the thermosetting resin after curing as particles.SELECTED DRAWING: Figure 1

Description

  The present invention uses a resin fine particle containing at least polyphenylene ether (PPE), a resin composition containing the resin fine particle, a prepreg composed of the resin composition and a substrate, and the prepreg suitable as an electronic substrate material. The present invention relates to a laminated board or 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 circuit board materials have low dielectric constant and low dielectric loss tangent in addition to traditionally required properties such as flame retardancy, heat resistance, and peel strength with copper foil. Therefore, various attempts have been made to improve the resin composition.

  Since PPE has a low dielectric constant and dielectric loss tangent, it is suitable as a printed wiring board material that meets 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 using a low molecular weight PPE having a number average molecular weight adjusted to about 2000 when a prepreg necessary for the production of a printed wiring board is manufactured. Yes. However, such a low molecular weight PPE increases the proportion of the phenolic hydroxyl group in the structure as the molecular weight decreases, so that a sufficiently low dielectric constant and a low dielectric loss tangent can be achieved. 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 finely divided 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, this method has poor adhesion between the epoxy resin and the PPE fine particles. In a heating process after substrate molding such as solder reflow, there is a possibility that the resin layer may be broken by an outgas component.

Japanese Patent No. 5779341 Special table 2015-522087 gazette

  Under the circumstances described above, the problem to be solved by the present invention is that when the thermosetting resin composition is cured, the adhesiveness (for example, the peel strength between layers in the multilayer board, or the curing of the thermosetting resin composition). Thermosetting resin composition capable of imparting to the cured product the low dielectric constant and dielectric loss tangent inherent in PPE and excellent soldering heat resistance without damaging the peel strength between the product and a metal foil such as copper foil) It is providing the prepreg which consists of a conductive resin composition and a base material, and the laminated board or printed wiring board manufactured using the said prepreg.

As a result of intensive studies and repeated experiments to solve the above-mentioned problems, the present inventors are composed of resin fine particles surface-treated with a metal alkoxide having a carbon-carbon unsaturated double bond group, which will be described later, and a thermosetting resin. When the thermosetting resin composition is cured, it has been found that the dielectric constant and dielectric loss tangent of the cured product can be reduced and the excellent solder heat resistance can be achieved without impairing the adhesion with the copper foil. It came to be completed.
That is, the present invention is as follows.
[1]
A resin fine particle composed of at least one kind of resin containing polyphenylene ether (PPE), and a thermosetting resin composition composed of a thermosetting resin,
The resin fine particles have the following formula:
{Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms or hydrogen, and Z represents an arylene group or a carbonyl group}
Surface-treated with a metal alkoxide having a carbon-carbon unsaturated double bond group having the structure shown in FIG.
The treatment amount of the metal alkoxide is 0.5 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 cured thermosetting resin. 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:
{Wherein, a is a natural number of 1 to 3, b is a natural number of 0 to 2, and R ₄ and R ₅ are each independently an alkyl group or branched alkyl group 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 silane coupling agent having the structure:
[4]
The thermosetting resin composition according to [2] or [3], wherein a treatment 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 number average molecular weight of the PPE is 8,000 to 30,000.
[8]
The content of the resin fine particles according to any one of [1] to [7], which is 5 parts by mass to 25 parts by mass with respect to a total of 100 parts by mass 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] or 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, PPE does not impair the adhesion (for example, the peel strength between layers in a multilayer board or the peel strength between a cured product of a curable resin composition and a metal foil such as a copper foil). A thermosetting resin composition capable of imparting a low dielectric constant and dielectric loss tangent and excellent solder heat resistance to a cured product, a prepreg composed of the thermosetting resin composition and a substrate, and the prepreg. A laminated board or a printed wiring board can be obtained.

FIG. 1A is an SEM image of the resin fine particles A subjected to surface treatment in Example 1, and FIG. 1B is an EDX chart of the resin fine particles A subjected to surface treatment. 2A is an SEM image of PPE that has not been subjected to surface treatment, and FIG. 2B is an EDX chart of PPE that has not been subjected to surface treatment. FIG. 3 is an SEM image of a laminate produced from the prepreg A obtained in Example 1. FIG. 4 is an SEM image of a laminate produced from the prepreg O obtained in Comparative Example 1.

  Hereinafter, although the embodiment of the present invention is described in detail, it is not intended that the present invention be limited to these embodiments.

  One embodiment 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 including at least PPE. When the resin fine particles are composed of a plurality of resins containing PPE, the respective resins may be uniformly compatible or mixed, and the structure in which the PPE covers the surface of the fine particles composed of other resins. You may be doing.

  The resin fine particles preferably contain 25 to 100 parts by mass, more preferably 50 to 100 parts by mass of PPE with respect to 100 parts by mass of the resin fine particles before being treated with the metal alkoxide. When the resin fine particles contain 25 parts by mass or more of PPE, when added to the thermosetting resin and cured, the cured product can be imparted with characteristics such as a low dielectric constant of the PPE.

The PPE contained in the resin fine particles is preferably the following general formula (1):
{Wherein 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, or a substituent. Represents an aryl group which may be substituted, an amino group which may have a substituent, a nitro group or a carboxyl group}
The repeating structural unit represented by is included.

  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) and the like, and 2,6-dimethylphenol and other phenols (for example, 2,3,6-phenylene ether) And a polyphenylene ether copolymer obtained by coupling 2,6-dimethylphenol and biphenols or bisphenols, and the like. A preferred example is poly (2,6-dimethyl-1,4-phenylene ether).

  In the present specification, 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, water absorption resistance, solder heat resistance, and adhesiveness (for example, peeling strength between layers in a multilayer board or curability) desired for printed wiring boards and the like This is preferable in that the peel strength between the cured product of the resin composition and the copper foil or the like is favorably provided. Further, it is preferable that the number average molecular weight of PPE is 100,000 or less because good workability can be obtained when PPE is made into fine particles by a method such as pulverization.

  Here, the number average molecular weight of the PPE contained in the resin fine particles is measured by gel permeation chromatography (GPC) by a method described later, and the standard expression from the relational expression between the molecular weight of the standard polystyrene sample measured under the same conditions and the elution time is The value measured in terms of polystyrene is defined 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 laminate) containing a cured product obtained by curing the thermosetting resin composition according to the present invention and a substrate. Is preferably 2.0 or less, more preferably 1.85 or less, and still more preferably, from the viewpoint of suppressing the increase in the dielectric constant and the viewpoint of suppressing the increase in the dielectric constant and dielectric loss tangent of the composite. 1.6 or less.

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

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

  Further, the PPE contained in the resin fine particles may be a reaction product of PPE and an unsaturated carboxylic acid or acid anhydride. Examples of the unsaturated carboxylic acid or acid anhydride 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 PPE and 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 purpose 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. Examples include ethylene, propylene, butadiene, isoprene, styrene, divinylbenzene, methacrylic acid, acrylic acid, methacrylic acid ester, acrylic acid ester, vinyl chloride, acrylonitrile, maleic anhydride, vinyl acetate, ethylene tetrafluoride, and other vinyls. A homopolymer of the compound and a copolymer of two or more kinds of vinyl compounds, polyamide, polyimide, polycarbonate, polyester, polyacetal, polyphenylene sulfide, polyethylene glycol and the like can be exemplified.

  The resin fine particles have an average particle size of 10 μm from the viewpoint of more uniformly dispersing the stress due to the heat change when applying a rapid heat change to the cured product of the thermosetting resin, such as a solder heat resistance test. The maximum particle size is preferably 30 μm or less. By using resin fine particles with an average particle size of 10 μm or less, excellent adhesion (for example, peel strength between layers in a multilayer board or peel strength between a cured product of a thermosetting resin composition and copper foil, etc.) is ensured. In addition, a more uniform dielectric constant and dielectric loss tangent can be given to the entire cured product.

  The resin fine particles are preferably uniformly dispersed in the cured thermosetting resin. When uneven distribution of the resin fine particles in the thermosetting resin after curing is remarkable, there is a possibility that the cured product may be broken starting from the uneven distribution portion. Moreover, as a method of confirming the dispersion state of the resin fine particles in the thermosetting resin, a method of confirming a cross section of the cured thermosetting resin composition with a scanning electron microscope (hereinafter referred to as “SEM”), etc. Is mentioned.

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

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

  The resin fine particles are surface-treated with a metal alkoxide, and are treated with 0.5 to 5 parts by mass of the metal alkoxide with respect to 100 parts by mass of the resin fine particles that are not surface-treated. More preferably, the treatment is performed at 1 to 4 parts by mass. By performing a surface treatment using a metal alkoxide by a 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 capable 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 is poor in reactivity with a thermosetting resin such as an epoxy resin. However, as described later, the solder heat resistance of the cured product of the thermosetting resin composition according to this embodiment is improved by treating the metal alkoxide having a carbon-carbon unsaturated double bond group in a hydrolyzed state. Therefore, by the surface treatment, either a chemical bond formed by condensation of metal alkoxides such as a hydroxyl group or a siloxane bond, a carbon-carbon unsaturated double bond group, or a combination thereof is exposed on the surface. It is estimated that the improvement of the wettability of the resin fine particles with respect to the thermosetting resin contributes to the improvement of the dispersibility of the resin fine particles in the thermosetting resin.

The metal alkoxide has the following formula:
{Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms or hydrogen, and Z represents an arylene group or a carbonyl group}
Although it does not specifically limit except having the carbon-carbon unsaturated double bond group of the structure shown in the following, for example, silicon alkoxide (hereinafter referred to as “silane coupling agent”), titanium alkoxide, aluminum alkoxide, zirconium alkoxide Etc.

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

  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 resin fine particles are surface-treated with a metal alkoxide, the metal alkoxide is preferably surface-treated after being previously dissolved in water. The treatment method is not particularly limited, and examples thereof include a dry treatment method, a wet treatment method, an integral blend method, and the like. The dry treatment method and the wet treatment method mainly include (1) preparing an aqueous solution of the compound, (2) mixing resin fine particles not subjected to surface treatment and the aqueous solution, (3) drying the mixture, and (4) It is processed by an 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 processing method, in the operation (2), a small amount of the aqueous solution is sprayed and mixed with the resin fine particles as an example while stirring. In the wet processing method, in the operation (2), resin fine particles are added to a large amount of the aqueous solution and dispersed in a slurry state. When drying in the operation (3), a dry processing method is preferable from the viewpoint of achieving a more uniform processing state with respect to the resin fine particles.

  About operation of said (1), you may adjust pH with an acid or an alkali with respect to water from a viewpoint of improving the stability after hydrolysis of a metal alkoxide. Further, from the viewpoint of dissolving the above-mentioned compound to prepare a homogeneous aqueous solution and improving the wettability with respect to resin fine particles not subjected to surface treatment to achieve a homogeneous treatment state, it can be mixed with water such as methanol. An organic solvent may be added.

  As for the operation (2), when dry processing is performed, it is possible to make the mist diameter of the aqueous solution to be sprayed finer, and to perform sufficient operations such as using a Henschel mixer to perform more uniform processing. It is preferable from the viewpoint that the state can be imparted to the resin fine particles.

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

  In 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, for example, a jet mill, a ball mill, a turbo mill, or the like can be used.

  The thermosetting resin composition used in the present embodiment includes the resin fine particles and a thermosetting resin. The thermosetting resin is not particularly limited, but epoxy resin, polyimide resin, bismaleimide triazine resin, phenol resin, bismaleimide, cyanate ester, polybutadiene or similar compound, triallyl isocyanurate, styrene Examples thereof include vinyl compounds typified by divinylbenzene and the like. Each of the resins may be used alone or in combination of two or more.

The thermosetting resin is preferably an epoxy resin. Examples of epoxy resins include, but are not limited to, 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, cresol novolacs. Type epoxy compound, naphthalene type epoxy compound, biphenyl type epoxy compound and the like. These may be used alone or in combination of two or more.
The epoxy resin preferably contains a curing agent. Although not particularly limited, examples of the curing agent include aliphatic polyamines, polyaminoamides, polymercaptans, aromatic polyamines, acid anhydrides, phenol novolac compounds, dicyandiamide, and cyanate ester compounds. These may be used alone or in combination of two or more.
The epoxy resin may include a curing accelerator. Although it does not specifically limit, A tertiary amine compound, a tertiary amine compound salt, an imidazole compound, a phosphine compound, a phosphonium compound salt etc. are mentioned as an example of a hardening accelerator. 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 to 25 parts by mass, more preferably 7 to 20 parts by mass with respect to a total of 100 parts by mass with the thermosetting resin. . When the thermosetting resin composition contains 5 parts by mass or more of resin fine particles, the resin composition can be given an effect of reducing dielectric constant or dielectric loss tangent, and the content of resin fine particles is 25 parts by mass or less. Thus, excellent solder heat resistance can be imparted without impairing adhesiveness (for example, peel strength between layers in a multilayer board or peel strength between a cured product of a curable resin composition and a metal foil such as a copper foil). .

  In this embodiment, the thermosetting resin composition includes, in addition to the resin fine particles and the thermosetting resin, for example, a reaction initiator or reaction accelerator for the thermosetting resin, a flame retardant, a silica filler, and other additives. Agents and the like can be preferably blended in a manner similar to these embodiments known in the art. Such formulations are also encompassed by the present disclosure. Moreover, a varnish, a prepreg, a metal-clad laminate, and a printed wiring board can be preferably formed using the thermosetting resin composition according to the present embodiment.

  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, and a polymer additive.

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

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

  The proportion of the thermosetting resin composition in the prepreg is preferably 30 parts by mass to 80 parts by mass, more preferably 40 parts by mass to 70 parts by mass with respect to 100 parts by mass of the total amount of prepreg. When the proportion is 30 parts by mass or more, excellent insulation reliability is obtained when the prepreg is used, for example, for forming an electronic substrate, and when the proportion 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 substrate and a metal foil are laminated can be formed. The laminate is preferably one in which the cured product composite and the metal foil are in close contact with each other, and is suitably used as a material for an electronic substrate. As the metal foil, for example, an aluminum foil and a copper foil can be used, and among them, the copper foil is preferable because of its low electric resistance. The cured product composite to be combined with the metal foil may be one sheet or a plurality of sheets, and the metal foil is overlapped on one side or both sides of the composite to be processed into a laminate according to the use. As a manufacturing method of a laminated board, after forming the composite_body | complex (for example, above-mentioned prepreg) comprised from a thermosetting resin composition and a base material, for example, and laminating this with metal foil, it is thermosetting resin. The method of obtaining the laminated board on which the hardened | cured material laminated body and metal foil are laminated | stacked by hardening a composition is mentioned. One particularly preferred application of the laminate is a printed wiring board. In the printed wiring board, it is preferable that at least a part of the metal foil is removed from the metal-clad laminate.

  Another aspect of the present invention provides a printed wiring board comprising a cured product of the thermosetting resin composition and a substrate. The printed wiring board of the present invention can typically be formed by a method of pressure and heat molding using the prepreg of the present invention described above. Examples of the substrate include the same materials as described above with respect to the prepreg. Since the printed wiring board of the present invention is formed using the thermosetting resin composition, it can have excellent insulation reliability and mechanical properties.

  Hereinafter, the present embodiment will be specifically described by way of examples. However, the present embodiment is not limited to the following examples.

  Each physical property described in the following examples, comparative examples, and test examples was 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 having a sample concentration of 0.2 w / vol% (solvent: chloroform), HLC-8220GPC (manufactured by Tosoh Corporation) was used as a measurement apparatus, and column: Shodex GPC KF-405L HQ × 3 (Showa Denko Co., Ltd.) (Manufactured by the company), eluent: chloroform, injection amount: 20 μL, flow rate: 0.3 mL / min, column temperature: 40 ° C., detector: RI.

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

(3) Water Absorption Rate of Laminate Plate The laminate plate was subjected to a water absorption acceleration test, and the water absorption rate was determined from the increased mass.
The laminate was cut into 50 mm squares to produce test pieces. After the test piece was dried at 105 ° C. for 60 minutes, the mass was measured to obtain the mass (g) before the acceleration test. Subsequently, the mass after the acceleration test was performed under the conditions of temperature: 121 ° C., pressure: 2 atm, and time: 4 hours, and the mass (g) after the acceleration test was measured.
Using the mass (g) before the acceleration test and the mass (g) after the acceleration test, the following formula:
Water absorption (mass%) = (mass before acceleration test−mass after acceleration test) / mass before acceleration test × 100
Then, the water absorption was calculated, and the average value of the measured values of the four test pieces was obtained.

(4) Solder heat resistance after water absorption test of laminate The solder heat test at 288 ° C. was performed using the laminate after measurement of water absorption as 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. A laminated board in which no swelling, peeling or whitening was confirmed even when immersed in a solder bath was evaluated as “◯ (good)”. Further, a laminate produced by any part of swelling, peeling and whitening by immersion in a solder bath was evaluated as “Δ (allowable)”, and when produced over the entire surface, the laminate was evaluated as “x (defective)”.

(5) Copper foil peel strength of laminate (peel strength N / mm)
The stress when peeling the copper foil of the copper clad laminate at a constant speed was measured. A copper-clad laminate using a 35 μm-thick copper foil (GTS-MP foil, manufactured by Furukawa Electric Co., Ltd.) produced by the method described later was cut into a size of 15 mm wide × 150 mm long, and an autograph (AG- 5000D (manufactured by Shimadzu Corporation) was used to measure the average value of the load when the copper foil was peeled off at a speed of 50 mm / min at an angle of 90 ° C. with respect to the removal surface, and the average value of the five measurements Asked.

(6) Particle size measurement of resin fine particles The average particle size and the maximum particle size of resin fine particles before and after the treatment were measured using a laser diffraction particle size measurement device (Microtrac MT3000-II manufactured by Microtrack Bell Co., Ltd.). Based on the data obtained by the operation described later, the smaller particle size is set to 0, the particle size at 50% particle volume distribution (d50) is the average particle size, and the particle size at 100% particle volume distribution (d100). Was the maximum particle size.
(Operation of particle size measurement)
A sample for measurement was prepared by adding 10 μg of fine resin particles, 10 ml of 0.2 wt% sodium hexametaphosphate aqueous solution, and several drops of 10 wt% Triton X-100 aqueous solution to a screw tube and sufficiently dispersing with an ultrasonic processor. Using this measurement sample, the measurement apparatus using water as a dispersion medium was used for 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) Laminate cross section observation by SEM The cross section of the laminate was observed using SEM (S-4100, manufactured by Hitachi High-Technologies Corporation). The observation sample was cut into a 10 mm square, embedded in a resin mixed with 90 parts by mass of Epomount main agent (manufactured by Refinetech Co., Ltd.) and 10 parts by mass of Epomount curing agent (manufactured by Refinetech Co., Ltd.), and room temperature. 1 day, and after cutting and polishing the embedded material so that the cross section of the sample can be observed, a sputtering apparatus using gold-palladium as a target (E-1020, manufactured by Hitachi, Ltd.) The cross section was prepared by conducting a conductive treatment. At the time of observation, the acceleration voltage was set to 20 kV and the observation was performed.

(8) Analysis of resin fine particles by EDX Analyzing resin fine particles before and after treatment with 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 affixed to a measurement sample stage, and conducting a conductive treatment on the sputtering apparatus using gold-palladium as a target. At the time of observation, the acceleration voltage was set to 20 kV and the measurement was performed.

<Example 1>
To 268 parts by mass of deionized water, 1.0 part by mass of acetic acid was added and dissolved. 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 stirring for 3 hours, 244.6 parts by mass of methanol was added to prepare 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 of 1.93) preliminarily pulverized with a jet mill to an average particle size of 4 μm and a maximum particle size of 11 μm Was added to the SUS container. While the treatment liquid A is put in a hand spray and the PPE is stirred, 47.4 parts by mass of the treatment liquid A is added so that the treatment amount of 3-methacryloxypropyltrimethoxysilane is 2 parts by mass with respect to 100 parts by mass of PPE. Sprayed into SUS container. Subsequently, after naturally drying for 1 day, it was dried with a dryer set at 100 ° C. for 8 hours. By crushing the sample in which the particles were aggregated by drying using a mortar, resin fine particles A (average particle size 4 μm, maximum particle size 13 μm) were obtained.

  When preparing the prepreg, the bisphenol A novolac epoxy is placed in the SUS container so that the resin fine particle content in the thermosetting resin composition is 15 parts by mass with respect to 100 parts by mass in total with the thermosetting 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% by mass Parts, bisphenol A type epoxy resin (1001B80, manufactured by Mitsubishi Chemical Corporation, containing 20% by mass of MEK) 7.3 parts by mass, bisphenol A novolac type resin (YLH129B65H, manufactured by Mitsubishi Chemical Corporation, containing 35% by mass of MEK) 38.0 parts by mass of 2-ethyl-4-methylimidazole (Shikoku Kasei Co., Ltd.) Butoxy ethanol solution (2-methoxyethanol and 50 wt% containing) 0.4 parts by weight, MEK34.1 parts by weight, and the resin fine particles A were added 15 parts by weight. A coating varnish A was obtained by carrying out a dispersion treatment at 8000 rpm for 10 minutes with a homogenizer (HM-300, manufactured by HSIANGTAI MACHINERY INDUSTRY) for 10 minutes.

  The coating varnish A was impregnated into a 0.1 mm thick E glass glass cloth (2116 style, manufactured by Asahi Schavel), the excess varnish was scraped off with a slit, and the solvent was removed by drying 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 in the same manner as in Example 1 except that 3-methacryloxypropyltrimethoxysilane was changed to 8-methacryloxyoctyltrimethoxysilane. Further, except that the resin fine particles A were changed to the resin fine particles B, a coating varnish B was obtained in the same manner as in Example 1 to obtain a prepreg B having a resin content of 56% by mass.

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

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

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

<Example 6>
Resin fine particles F (average particle diameter) were obtained 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 was 5 parts by mass. 4 μm, maximum particle size 14 μm). Further, except that the resin fine particles A were changed to the resin fine particles F, a coating varnish F was obtained in the same manner as in Example 1 to obtain a prepreg F having a resin content of 56% by mass.

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

<Example 8>
The average particle size is 9 μm and the maximum particle size is 26 μm, and the amount of the treatment liquid is 118.4 parts by mass so that the treatment amount of 3-methacryloxypropyltrimethoxysilane is 5 parts by mass. Except for changing, resin fine particles H (average particle size 10 μm, maximum particle size 30 μm) were obtained in the same manner as in Example 1. Moreover, the coating varnish H was obtained by the same method as Example 1 except having changed the resin fine particle A into the resin fine particle H, and the prepreg H with a resin content of 56 mass% was obtained.

<Example 9>
When the prepreg was produced, the amount of resin fine particles A added was 4.5 so that the resin fine particle content 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 addition amount of the mass part and MEK 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 is produced, the amount of resin fine particles A added is 28.3 so that the resin fine particle content in the thermosetting resin composition is 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 addition amount of the mass part and MEK 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 was changed to S201A (manufactured by Asahi Kasei Corporation, number average molecular weight 25,200, average number of phenolic hydroxyl groups per molecule 1.99, average particle size 5 μm, maximum particle size 13 μm). In the same manner, resin fine particles K (average particle size 5 μm, maximum particle size 15 μm) were obtained. Further, except that the resin fine particles A were changed to resin fine particles K, a coating varnish K was obtained in the same manner as in Example 1 to obtain a prepreg K having a resin content of 56% by mass.

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

<Comparative Example 1>
A coating varnish O was obtained in the same manner as in Example 1 except that a coating varnish was obtained using PPE not subjected to surface treatment 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 diameter) were obtained 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 was 6 parts by mass. 5 μm, maximum particle size 14 μm). Moreover, the coating varnish P was obtained by the same method as Example 1 except having changed the resin fine particle A into the resin fine particle P, and the prepreg P with a resin content of 56 mass% was obtained.

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

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

<Comparative Example 7>
A coating varnish U was obtained in the same manner as in Example 1 except that the resin fine particles were not added and the MEK addition amount was changed to 15.3 parts by mass, 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 electrical characteristics (dielectric constant, dielectric loss tangent), water absorption, solder heat resistance after water absorption The copper foil peel strength was comparatively evaluated.

A sample for measuring dielectric constant and dielectric loss tangent and a sample for observing the cross section of the laminate were prepared by the following method. Eight prepregs obtained in the examples or comparative examples were stacked, 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. While pressing at a rate of 5 ° C./min, vacuum pressing is performed under the condition of a pressure of 30 kg / cm ^2. When the temperature reaches 195 ° C., the pressure is maintained at 195 ° C. and the pressure is 30 kg / cm ² for 60 minutes. The laminated board was produced by performing. The laminate was cut into a 100 mm square, processed into the above-mentioned test piece size, and used as a dielectric constant and dielectric loss tangent measurement sample and a cross-sectional observation sample.

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 having a thickness of 12 μm (GTS foil, manufactured by Furukawa Electric Co., Ltd.) was stacked on the top and bottom. Vacuum pressing is performed under conditions of a pressure of 5 kg / cm ² while heating in minutes, and when reaching 130 ° C., vacuum pressing is performed under conditions of a pressure of 30 kg / cm ² while heating at a heating rate of 5 ° C./min. When the temperature reached 195 ° C., a double-sided copper clad laminate was obtained by performing 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 is cut into a 100 mm square, the copper foil is removed by etching, and after processing into the above test piece size, a sample for evaluating the water absorption rate and the solder heat resistance after the water absorption test is obtained. It was.

A sample for measuring the copper foil peel strength was prepared by the following method. Two prepregs obtained in Examples or Comparative Examples were stacked, and a copper foil (GTS-MP foil, manufactured by Furukawa Electric Co., Ltd.) having a thickness of 35 μm was stacked on the top and bottom, and the temperature rising rate from room temperature was 2.5. Perform vacuum pressing under the condition of pressure 5 kg / cm ² while heating at ℃ / min, and perform the vacuum pressing under the condition of pressure 30 kg / cm ² while heating at the heating rate of 5 ° C / min when reaching 130 ° C. 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. After processing this double-sided copper-clad laminate into the above-mentioned test piece size, it was used as a sample for measuring copper foil peel strength.

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

The resin fine particles A and PPE not subjected to surface treatment were analyzed by EDX. An SEM image and an EDX chart of the resin fine particles A and PPE not subjected to surface treatment are shown in FIGS. 1 and 2, respectively.
(Contrast of FIG. 1 and FIG. 2)
When the two samples were compared, a silicon signal derived from 3-methacryloxypropyltrimethoxysilane was confirmed only from the resin fine particles A.

Moreover, the cross section of the sample produced for the measurement of the above-mentioned dielectric constant and dielectric loss tangent using prepreg A and prepreg O was photographed with SEM. Cross-sectional SEM images of a sample prepared from prepreg A and a sample prepared from prepreg O are shown in FIGS. 3 and 4, respectively.
(Contrast of FIG. 3 and FIG. 4)
When the two samples were compared, it was confirmed that in the sample prepared from prepreg A, the resin fine particles were uniformly dispersed in the epoxy resin.

Claims (11)

A resin fine particle composed of at least one kind of resin containing polyphenylene ether (PPE), and a thermosetting resin composition composed of a thermosetting resin,
The resin fine particles have the following formula:
{Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms or hydrogen, and Z represents an arylene group or a carbonyl group}
Surface-treated with a metal alkoxide having a carbon-carbon unsaturated double bond group having the structure shown in FIG.
The treatment amount of the metal alkoxide is 0.5 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 cured thermosetting resin. ing,
The thermosetting resin composition.   The thermosetting resin composition according to claim 1, wherein the metal alkoxide is a silane coupling agent. The silane coupling agent has the following formula:
{Wherein, a is a natural number of 1 to 3, b is a natural number of 0 to 2, and R ₄ and R ₅ are each independently an alkyl group or branched alkyl group 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 claim 2, which is at least one silane coupling agent having the structure:   The thermosetting resin composition according to claim 2 or 3, wherein a treatment 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 claim 1, wherein the thermosetting resin is an epoxy resin.   The thermosetting resin composition according to claim 1, 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 6, wherein the number average molecular weight of the PPE is 8,000 to 30,000.   The thermosetting according to any one of claims 1 to 7, wherein a content of the resin fine particles is 5 to 25 parts by mass with respect to 100 parts by mass in total of the resin fine particles and the thermosetting resin. Resin composition.   A prepreg comprising the thermosetting resin composition according to claim 1 and a base material.   A metal-clad laminate formed by the thermosetting resin composition according to any one of claims 1 to 8, or the prepreg according to claim 9, 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 10.