JP2011174035A - Resin composition and molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which provides a molding having improved surface smoothness when the composition is laminated on a member having a hole or unevenness in a surface thereof, and to provide a molding. <P>SOLUTION: The resin composition contains an epoxy resin, an active ester compound, first silica having a mean particle diameter of 0.1-10 &mu;m, and second silica having a mean particle diameter of &ge;1 nm and &lt;100 nm. The molding is obtained by molding the composition into a sheet-like shape. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a resin composition containing an epoxy resin, a curing agent and silica, and a molded body using the resin composition.

  Conventionally, various resin compositions have been used to form electronic components such as laminates and printed wiring boards.

  As an example of the resin composition, the following Patent Document 1 includes a resin composition containing an epoxy resin, an epoxy resin curing agent, a phenoxy resin, and an inorganic filler having an average particle diameter of 0.01 to 2 μm. Is disclosed. Furthermore, here, a resin composition including an epoxy resin, an epoxy resin curing agent, and an inorganic filler having an average particle diameter of 0.1 to 10 μm is also disclosed.

  In patent document 1, each layer of the multilayer film which has a laminated structure of two layers is formed using two types of above-mentioned different resin compositions. It is described that this multilayer film is satisfactorily embedded in a gap or the like provided on the substrate.

  Patent Document 2 below discloses a resin composition containing a compound having a heterocyclic group, an epoxy resin, and an active ester compound. A filler can be added to this resin composition. Here, it is described that a cured product having a low water absorption rate, excellent dielectric characteristics, and high heat resistance and dimensional stability can be obtained.

JP 2008-302677 A JP 2006-028498 A

  In patent document 1, since two types of resin compositions are prepared and the multilayer film is produced, there exists a problem that production of a multilayer film takes time and cost becomes high.

  In the resin composition described in Patent Document 2, when the resin composition is applied onto a substrate having holes or irregularities on the surface thereof, the hole filling property or the irregularity following property is low, and the smoothness of the upper surface of the resin composition May be low. Furthermore, even when the resin composition described in Patent Document 2 is formed into a sheet shape to obtain a molded body, the obtained molded body has low filling property or unevenness followability, and the top surface of the resin composition is low. Smoothness may be low.

  An object of the present invention is to provide a resin composition that makes it possible to obtain a molded article capable of improving the smoothness of the surface when laminated on a member having holes or irregularities on the surface, and uses the resin composition. It is to provide a molded body.

  According to a wide aspect of the present invention, an epoxy resin, an active ester compound, a first silica having an average particle size of 0.1 μm or more and 10 μm or less, and a second silica having an average particle size of 1 nm or more and less than 100 nm And the content of the second silica with respect to 100 parts by weight of the first silica is 0.6 to 30 parts by weight.

  In a specific aspect of the resin composition according to the present invention, the total content of the first and second silicas in 100% by weight of the resin composition (excluding the solvent when the resin composition includes a solvent). Is 25 to 80% by weight, and the content of the second silica is 0.45 to 24.5 parts by weight with respect to a total of 100 parts by weight of the resin components contained in the resin composition.

  In another specific aspect of the resin composition according to the present invention, the total content of the first and second silicas in 100% by weight of the resin composition (excluding the solvent when the resin composition includes a solvent). The amount is 45 to 75% by weight.

  In still another specific aspect of the resin composition according to the present invention, the content of the second silica is 4 to 18 parts by weight with respect to a total of 100 parts by weight of the resin components contained in the resin composition. is there.

  In another specific aspect of the resin composition according to the present invention, the content of the second silica is 0.8 to 30 parts by weight with respect to 100 parts by weight of the first silica.

  In still another specific aspect of the resin composition according to the present invention, the content of the second silica is 2 to 15 parts by weight with respect to 100 parts by weight of the first silica.

  In another specific aspect of the resin composition according to the present invention, the content of the second silica is 3 to 15 parts by weight with respect to 100 parts by weight of the first silica.

  The first and second silicas are preferably treated with a silane coupling agent. At least one of the first and second silicas is preferably treated with an epoxy silane coupling agent.

  The molded body according to the present invention is a molded body in which the resin composition configured according to the present invention is formed into a sheet shape.

  On the specific situation with the molded object which concerns on this invention, the thickness of a molded object is 5-100 micrometers.

  Since the resin composition according to the present invention includes an epoxy resin, an active ester compound, a first silica having an average particle size of 0.1 μm or more and 10 μm or less, and a second silica having an average particle size of 1 nm or more and less than 100 nm, Furthermore, since content of the 2nd silica with respect to 100 weight part of 1st silica is 0.6-30 weight part, when it laminates | stacks on the member which has a hole or an unevenness | corrugation in the surface, it improves the smoothness of the surface. A sheet-like molded body that can be obtained can be obtained.

  Details of the present invention will be described below.

(Resin composition)
The resin composition according to the present invention comprises an epoxy resin, an active ester compound, a first silica having an average particle size of 0.1 μm or more and 10 μm or less, and a second silica having an average particle size of 1 nm or more and less than 100 nm. Including. In the resin composition according to the present invention, the content of the second silica with respect to 100 parts by weight of the first silica is 0.6 to 30 parts by weight.

  Since the resin composition according to the present invention has the above composition, when the resin composition and a molded body obtained by molding the resin composition into a sheet are laminated on a member having holes or irregularities on the surface, the resin composition or The smoothness of the surface of a molded object can be improved. In addition, since the resin composition according to the present invention has the above composition, it has excellent shape followability, and can improve the filling property or uneven followability of the resin composition and a molded body obtained by molding the resin composition into a sheet shape. it can. For example, when a resin composition or a molded body is laminated on a member having a hole such as a via hole or a through hole on the surface, or a member having an uneven surface on the surface by a wiring circuit or the like, the resin composition or the molded body is formed in the hole or the recess. Can be embedded sufficiently, and the smoothness of the surface of the resin composition or molded article can be further improved. Furthermore, the storage stability of the resin composition and the molded body can be enhanced.

  When the average particle diameter of the second silica is 1 nm or more, since the secondary aggregation of the silica does not occur so much, the embedding property of the resin composition or the molded body can be improved. When the average particle diameter of the second silica is less than 100 nm, the embedding property of the resin composition or the molded body can be improved, and the smoothness of the surface of the resin composition or the molded body can be further increased. The average particle diameter of the second silica is more preferably 3 nm or more and less than 50 nm. The average particle diameter of the second silica is more preferably less than 25 nm.

  The embedding property of a resin composition or a molded object can be improved as the average particle diameter of a 1st silica is 0.1 micrometer or more. The smoothness of the surface of a resin composition or a molded object can be improved as the average particle diameter of a 1st silica is 10 micrometers or less. The average particle diameter of the first silica is preferably 0.3 μm or more and less than 5 μm.

  The content of the second silica with respect to 100 parts by weight of the first silica is 0.6 to 30 parts by weight. When the content of the second silica is 0.6 parts by weight or more, the embedding property of the resin composition or the molded body can be increased, and the smoothness of the surface of the resin composition or the molded body can be further increased. . When the content of the second silica is 30 parts by weight or less, the embedding property in the wiring pattern and the filling property in a hole such as a via hole or a through hole can be improved. Moreover, the storage stability of the resin composition can be improved. The preferred lower limit of the content of the second silica with respect to 100 parts by weight of the first silica is 0.8 parts by weight, the more preferred lower limit is 1 part by weight, the still more preferred lower limit is 2 parts by weight, and the particularly preferred lower limit is 2.5 parts by weight. The most preferred lower limit is 3 parts by weight, the preferred upper limit is 25 parts by weight, the more preferred upper limit is 20 parts by weight, the still more preferred upper limit is 15 parts by weight, and the most preferred upper limit is 12 parts by weight.

  The content of the second silica is preferably 0.8 to 30 parts by weight with respect to 100 parts by weight of the first silica. In addition, from the viewpoint of further improving the embedding property and surface smoothness of the resin composition or molded body, the content of the second silica is 2 to 15 parts by weight with respect to 100 parts by weight of the first silica. It is more preferable that it is 3 to 15 parts by weight.

  It is preferable that the content of the second silica is 0.45 to 30 parts by weight with respect to 100 parts by weight of the total resin components contained in the resin composition. When the content of the second silica is 0.45 parts by weight or more, the embedding property of the resin composition or the molded body can be further improved, and the surface smoothness of the resin composition or the molded body is further improved. It can be further enhanced. When the content of the second silica is 30 parts by weight or less, the filling property to holes such as via holes or through holes and the embedding property to wiring patterns can be further enhanced. Moreover, the storage stability of a resin composition or a molded object can be improved further. The more preferable lower limit of the content of the second silica is 0.6 parts by weight, the still more preferable lower limit is 1 part by weight, and the further preferable lower limit is 100 parts by weight of the total resin components contained in the resin composition. 1.5 parts by weight, the most preferred lower limit is 4 parts by weight, the more preferred upper limit is 24.5 parts by weight, the still more preferred upper limit is 18 parts by weight, and the most preferred upper limit is 13 parts by weight.

  In addition, the said resin component contains an epoxy resin and an active ester compound, and the other resin component mix | blended as needed. The resin component includes a curing accelerator. The resin component does not include the first and second silica. When the resin composition contains a solvent, the resin component does not contain a solvent.

[Epoxy resin]
The epoxy resin refers to an organic compound having at least one epoxy group. As for the said epoxy resin, only 1 type may be used and 2 or more types may be used together.

  The epoxy resin is not particularly limited. A conventionally well-known epoxy resin can be used as this epoxy resin. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, biphenol type epoxy resin, naphthalene type epoxy resin, phenol aralkyl type epoxy resin, and naphthol aralkyl type epoxy. Examples thereof include resins, dicyclopentadiene type epoxy resins, triazine skeleton-containing epoxy resins and anthracene type epoxy resins.

[Curing agent]
The resin composition according to the present invention contains an active ester compound as a curing agent.

  The active ester compound preferably has 2 or more ester groups, and more preferably 3 or more ester groups. The active ester compound is described in, for example, JP-A Nos. 2002-12650 and 2004-169021. As for the said active ester compound, only 1 type may be used and 2 or more types may be used together.

  The active ester compound can be obtained by a conventionally known method. The active ester compound can be obtained, for example, by a Schotten-Baumann reaction using a carboxylic acid having two or more ester bonds in the molecule and an aromatic hydroxy compound. Examples of the carboxylic acid having two or more ester bonds in the molecule include acetic acid, propionic acid, butyric acid and benzoic acid. Examples of the aromatic hydroxy compound include 1,3,5-trihydroxybenzene.

  Specific examples of the active ester compound include di (α-naphthyl) isophthalate. Examples of commercial products of the active ester compound include “EXB-9451”, “EXB-9451-65T”, “EXB-9460S”, and “EXB-9460S-65T” manufactured by DIC.

  The content of the active ester compound is preferably in the range of 50 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin. The dielectric property of the hardened | cured material of a resin composition can be improved as content of the said active ester compound is 50 weight part or more.

  The resin composition according to the present invention may contain a curing agent other than the active ester compound in addition to the active ester compound. As for said other hardening | curing agent, only 1 type may be used and 2 or more types may be used together.

  As said other hardening | curing agent, a phenol compound, an amine compound, an acid anhydride, a dicyandiamide, etc. are mentioned.

[Curing accelerator]
From the viewpoint of uniformly curing the resin composition and the molded body, the resin composition according to the present invention preferably includes a curing accelerator. The curing accelerator is not particularly limited. As for the said hardening accelerator, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of more uniformly curing the resin composition and the molded body, the resin composition preferably contains an imidazole compound as the curing accelerator, and the curing accelerator is preferably an imidazole compound.

  Specific examples of the imidazole compound include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 -Benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 -Cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ') -Ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4 '-Methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2- Examples include phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole.

  Furthermore, from the viewpoint of further increasing the surface smoothness of the resin composition and the molded body, and from the viewpoint of further reducing the surface roughness of the cured surface of the resin composition and the molded body, the resin composition is N, N-dimethyl-4-aminopyridine (DMAP) is preferably included as the curing accelerator, and the curing accelerator is preferably N, N-dimethyl-4-aminopyridine.

  The present inventors include N, N-dimethyl-4-aminopyridine as a curing accelerator in addition to the above components, so that the resin composition and the molded body have holes or irregularities on the surface. When it is laminated on the member having the above, the smoothness of the surface of the resin composition or the molded body can be further improved, and the surface roughness of the cured surface of the resin composition and the molded body is further reduced. I found that I can do it. In particular, the use of N, N-dimethyl-4-aminopyridine can reduce the arithmetic average roughness Ra of the surface of the cured product.

  The content of the curing accelerator is preferably in the range of 0.01 to 2 parts by weight with respect to 100 parts by weight of the active ester compound. A resin composition and a molded object can be hardened more uniformly as content of the said hardening accelerator is 0.01 weight part or more. When the content of the curing accelerator is 2 parts by weight or less, the resin composition and the molded body are not excessively cured during storage, and the storage stability of the resin composition and the molded body can be improved.

  Moreover, it is preferable that content of the said N, N-dimethyl-4-aminopyridine exists in the range of 0.01-2 weight part with respect to 100 weight part of said active ester compounds. When the content of the N, N-dimethyl-4-aminopyridine is within the above range, the surface smoothness of the resin composition or the molded body and the surface roughness of the cured surface of the resin composition and the molded body are reduced. It can be made even smaller.

  The resin composition according to the present invention may contain a curing accelerator other than the imidazole compound and N, N-dimethyl-4-aminopyridine. Only 1 type may be used for this other hardening accelerator, and 2 or more types may be used together.

[filler]
The resin composition according to the present invention includes, as a filler, a first silica having an average particle size of 0.1 μm or more and 10 μm or less and a second silica having an average particle size of 1 nm or more and less than 100 nm.

  By combining the specific first silica having a relatively large average particle diameter with the specific second silica having a relatively small average particle diameter, and using the epoxy resin and the active ester compound, holes or irregularities can be formed. When laminated on a member on the surface, the surface smoothness of the resin composition can be improved. Moreover, the hole filling property or uneven | corrugated followable | trackability of a resin composition and a molded object can be improved. For example, when a resin composition or a molded body is laminated on a member having a hole such as a via hole or a through hole on the surface, or a member having an uneven surface on the surface by a wiring circuit or the like, the resin composition or the molded body is formed in the hole or the recess. Can be embedded sufficiently.

  A median diameter (d50) value of 50% is adopted as the average particle diameter of the first and second silicas. The average particle size can be measured using a laser diffraction / scattering particle size distribution measuring apparatus.

  From the viewpoint of further improving the hole filling property or unevenness followability by increasing the dispersibility of the first and second silica in the resin composition, each of the first and second silicas is treated with a coupling agent. Preferably it is. Examples of the coupling agent include silane coupling agents, titanate coupling agents, and aluminum coupling agents.

  From the viewpoint of further enhancing the dispersibility of the first and second silica in the resin composition, the coupling agent is preferably a silane coupling agent. Examples of the silane coupling agent include amino silane, imidazole silane, and epoxy silane. Furthermore, examples of the silane coupling agent include vinyl silane, phenylamino silane, and hexamethyldisilazane. By using vinylsilane, phenylaminosilane, or hexamethyldisilazane, the dispersibility of the first and second silicas is improved, and a resin composition capable of obtaining a molded product having more excellent surface smoothness and embedding property. Is obtained. From the viewpoint of further enhancing the dispersibility of the first and second silicas in the resin composition, at least one of the first and second silicas is preferably treated with an epoxy silane coupling agent. More preferably, the first silica is treated with an epoxy silane coupling agent. The epoxy silane coupling agent is a silane coupling agent having an epoxy group, for example, epoxy silane. When epoxy silane is used, the breaking strength of the cured product of the resin composition and the cured product of the molded body is greater than when silane coupling agents are used.

  From the viewpoint of further improving the smoothness of the surface of the resin composition or the molded body, as well as hole filling or unevenness followability, in 100% by weight of the resin composition (excluding the solvent when the resin composition contains a solvent), The total content of the first and second silica is preferably in the range of 25 to 80% by weight. In 100% by weight of the resin composition (excluding the solvent when the resin composition contains a solvent), the more preferable lower limit of the total content of the first and second silicas is 35% by weight, and the more preferable lower limit is 45%. %, A more preferred upper limit is 75% by weight, and a still more preferred upper limit is 65% by weight.

(Other ingredients)
For the purpose of improving impact resistance, heat resistance, resin compatibility, workability, etc., the resin composition is provided with a colorant, an antioxidant, an ultraviolet degradation inhibitor, an antifoaming agent, a thickener, and thixotropic properties. You may add other resin other than an agent and the said epoxy resin.

  Examples of other resins include polyphenylene ether resin, phenoxy resin, polyacetal resin, polybutyral resin, divinyl benzyl ether resin, polyarylate resin, diallyl phthalate resin, polyimide resin, benzoxazine resin, benzoxazole resin, bismaleimide resin, cyanate Examples thereof include resins and acrylate resins.

  The resin composition according to the present invention may contain a solvent. Examples of the solvent include acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, toluene, xylene, methyl ethyl ketone, Examples thereof include N, N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, n-hexane, cyclohexane, cyclohexanone, and naphtha as a mixture. As for the said solvent, only 1 type may be used and 2 or more types may be used together.

  The resin composition containing a solvent can be used as a varnish. The viscosity of the varnish can be adjusted by adjusting the solvent content according to the application. The content of the solvent is preferably in the range of 10 to 1000 parts by weight with respect to 100 parts by weight of the solid content of the resin composition.

(Molded body)
A molded body can be obtained by molding the resin composition according to the present invention into a sheet shape.

  The method for forming the resin composition into a sheet is not particularly limited. As this method, for example, using an extruder, the above resin composition is melt-kneaded, extruded, and then molded into a sheet shape with a T die or a circular die, or a resin composition containing a solvent. Examples thereof include a casting molding method in which a casting is performed to form a sheet, or other conventionally known sheet molding methods. Of these, the extrusion molding method or the casting molding method is preferable because the thickness can be reduced.

  From the viewpoint of enhancing the handleability of the molded body or forming a cured product layer having an appropriate thickness, the thickness of the molded body is preferably in the range of 5 to 100 μm.

(Hardened product of resin composition and molded body)
In order to form fine irregularities on the surface of the cured product on which the metal layer is formed, the resin composition or the molded body may be pre-cured to obtain a semi-cured cured product. In order to pre-cure appropriately, it is preferable to cure the resin composition or the molded body by heating at 130 to 190 ° C. for 30 minutes or more.

  When the pre-curing temperature is lower than 130 ° C., the resin composition and the molded body are not sufficiently cured, so that the unevenness of the surface of the cured product after the roughening treatment becomes large. When the preliminary curing temperature is higher than 190 ° C., the curing reaction of the resin composition and the molded body tends to proceed rapidly. For this reason, the degree of curing tends to be partially different, and a rough portion and a dense portion are likely to be formed. As a result, the unevenness of the surface of the cured product after the roughening treatment is increased. When the pre-curing time is shorter than 30 minutes, the resin composition and the molded body are not sufficiently cured, so that the unevenness of the surface of the cured product after the roughening treatment becomes large. Since productivity can be improved, it is preferable that pre-curing time is 1 hour or less.

  In order to form fine irregularities on the surface of the obtained cured product, the cured product is roughened. The cured product is preferably subjected to a swelling treatment before the roughening treatment. However, the cured product is not necessarily subjected to the swelling treatment.

  As the swelling treatment method, for example, a method of treating a cured product with an aqueous solution or an organic solvent dispersion solution of a compound mainly composed of ethylene glycol or the like is used. Specifically, the swelling treatment is carried out by treating the cured product with a 40 wt% ethylene glycol aqueous solution or the like at a treatment temperature of 30 to 85 ° C. for 1 to 20 minutes.

  For the roughening treatment, for example, a chemical oxidizing agent such as a manganese compound, a chromium compound, or a persulfuric acid compound is used. These chemical oxidizers are used as an aqueous solution or an organic solvent dispersion after water or an organic solvent is added.

  Examples of the manganese compound include potassium permanganate and sodium permanganate. Examples of the chromium compound include potassium dichromate and anhydrous potassium chromate. Examples of the persulfate compound include sodium persulfate, potassium persulfate, and ammonium persulfate.

  The roughening treatment method is not particularly limited. As the roughening treatment method, for example, using a 30 to 90 g / L permanganate or permanganate solution and a 30 to 90 g / L sodium hydroxide solution, a treatment temperature of 30 to 85 ° C. and a condition of 1 to 10 minutes And the method of processing hardened | cured material once or twice is suitable. When the number of roughening treatments is large, the roughening effect is large. However, if the number of times of roughening treatment exceeds 3, the roughening effect may be saturated, or the resin component on the surface of the cured product is scraped more than necessary, and the silica component is detached from the surface of the cured product. It becomes difficult to form holes having the shape.

(Use of resin composition and molded body)
Applications of the resin composition and the molded body according to the present invention are not particularly limited. The resin composition is, for example, a substrate material for forming a core layer or a buildup layer of a multilayer substrate, an adhesive sheet, a laminate, a copper foil with resin, a copper clad laminate, a TAB tape, a printed board, a prepreg, or It is suitably used for varnishes and the like.

  The resin composition and the molded body according to the present invention are applied or laminated by heating and pressing a substrate material having a concavo-convex pattern, a through hole or a via hole on a surface thereof, for example, in a multilayer printed board or a component built-in printed board. Can be used for

  Hereinafter, the present invention will be specifically described by giving examples and comparative examples. The present invention is not limited to the following examples.

  In the examples and comparative examples, the following materials were used.

(Epoxy resin)
Epoxy resin (phenol novolac type epoxy resin, “Epicoat 154” manufactured by Japan Epoxy Resin Co., Ltd.)
Epoxy resin (bisphenol A type epoxy resin, “RE-410S” manufactured by Nippon Kayaku Co., Ltd.)

(Curing agent)
Active ester compound solution (“EXB-9460S-65T” manufactured by DIC, active ester compound (solid content) 65 wt%, toluene 35 wt%)

(Curing accelerator)
Imidazole compound (2-phenyl-4-methylimidazole, “2P4MZ” manufactured by Shikoku Chemicals)
Imidazole compound (2-phenyl-4-methyl-5-hydroxymethylimidazole, “2P4MHZ-PW” manufactured by Shikoku Kasei Co., Ltd.)
DMAP (N, N-dimethyl-4-aminopyridine, manufactured by Wako Pure Chemical Industries, Ltd.)

(Silica component)
First silica-containing slurry A:
First silica (silica (“Advertex” SC2050-MTF ”, average particle size 0.5 μm) is epoxy silane (3-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.“ KBM-403 ”) The first silica-containing slurry containing 100 wt% silica and having been surface treated with 1.5 parts by weight of epoxysilane)

First silica-containing slurry B:
First silica-containing slurry containing first silica (silica (“SC2050-MTF” manufactured by Admatechs, average particle size 0.5 μm))

First silica-containing slurry C:
The first silica (silica (“Advertex Corporation SC2050-MTF”, average particle size 0.5 μm) is made of vinylsilane (vinyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. “KBM-1003”) 100% silica by weight. First silica-containing slurry containing 1.5 parts by weight of vinylsilane with respect to the surface)

First silica-containing slurry D:
The first silica (silica (“Advertex Corporation SC2050-MTF”, average particle size 0.5 μm) is phenylaminosilane (N-phenyl-3-aminopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. “KBM-573”). )), The first silica-containing slurry containing 100% by weight of silica and surface-treated with 1.5 parts by weight of epoxysilane.

First silica-containing slurry E:
The first silica (silica (“Advertex Corporation SC2050-MTF”, average particle size 0.5 μm) is converted into silica by aminosilane (3-aminopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. “KBM-903”). First silica-containing slurry containing 100% by weight of a surface-treated epoxy silane (1.5 parts by weight)

  The second silica (silica (“SX007-MDF” manufactured by Admatechs Co., Ltd., average particle diameter of 0.01 μm) is converted to 100 weight silica by phenylsilane (phenyltrimethoxysilane, “KBM-103” manufactured by Shin-Etsu Chemical Co., Ltd.). 2nd silica containing slurry containing what was surface-treated by 1.5 weight part of phenylsilane with respect to part

(solvent)
Methyl ethyl ketone (manufactured by Sankyo Chemical Co., Ltd.)

Example 1
To 50 parts by weight of methyl ethyl ketone, 15.00 parts by weight of an epoxy resin (phenol novolac type epoxy resin, “Epicoat 154” manufactured by Japan Epoxy Resin Co., Ltd.), 47.50 parts by weight of the first silica-containing slurry in solids, The silica-containing slurry of No. 2 was added with 2.50 parts by weight as a solid content, and stirred at 1200 rpm for 1 hour using a stirrer.

  Next, 34.70 parts by weight of an active ester compound (“EXB-9460S-65T” manufactured by DIC) in solid content was further added and stirred at 1200 rpm for 90 minutes using a stirrer.

  Thereafter, 0.30 part by weight of an imidazole compound (2-phenyl-4-methylimidazole, “2P4MZ” manufactured by Shikoku Kasei Co., Ltd.) was further added, followed by stirring at 1200 rpm for 10 minutes using a stirrer to obtain a resin composition.

  The resin composition was coated on a polyethylene terephthalate film using a coating machine. The solvent was volatilized by drying in a gear oven at 100 ° C. for 3 minutes. In this manner, a sheet-like molded body having a thickness of 50 μm was obtained on the PET film.

(Examples 2-12 and Comparative Examples 1-5)
A resin composition and a molded body were obtained in the same manner as in Example 1 except that the type and blending amount of the materials used were changed as shown in Table 1 below.

(Evaluation)
(1) Embeddability 1
A copper-clad laminate (a laminate of a glass epoxy substrate having a thickness of 150 μm and a copper foil having a thickness of 25 μm) is provided with 25 holes having a diameter of 150 μm and a depth of 50 μm on a straight line and the distance between the centers of adjacent holes. Was made to be 500 μm to obtain a perforated substrate.

  The molded bodies (thickness 50 μm) obtained in the examples and comparative examples were stacked with a perforated substrate, and a vacuum pressurization laminator machine (model number MVLP-500) manufactured by Meiki Seisakusho was used. Second, pressurization was performed at a press pressure of 0.8 MPa for 20 seconds, and a laminating and pressing temperature of 90 ° C. After cooling at room temperature, the polyethylene terephthalate film was peeled off. Thus, the laminated body by which the molded object was laminated | stacked on the perforated board | substrate was obtained.

  In the obtained laminate, the degree of dents on the upper surface of the molded body portion corresponding to the holed portion of the perforated substrate was measured using the molded body portion corresponding to the holeless substrate as a standard. The unevenness was measured with a surface roughness meter (trade name “SJ-301”, manufactured by Mitutoyo Corporation).

  Of the 25 parts of the molded body corresponding to the holed portion of the perforated substrate, the total number T1 of the places where there is no dent and the places where there is a dent but the depth of the dent on the center line of the hole is within 1 μm The embedding property 1 was determined according to the following criteria. The larger the total number T1, the better the embedding in the hole.

[Criteria for Embedding 1]
A: Total number T1 is 25
B: Total number T1 is 23-24
C: Total number T1 is 20-22
D: Total number T1 is 0 to 19

(2) Embeddability 2
A copper-clad laminate (a laminate of a 150 μm thick glass epoxy substrate and a 25 μm thick copper foil) was prepared. The copper foil was etched to produce 26 copper patterns having an L / S of 50 μm / 50 μm and a length of 1 cm to obtain an uneven substrate.

  The molded bodies (thickness: 50 μm) obtained in the examples and comparative examples were stacked with the concavo-convex substrate, and a vacuum pressurization laminator machine (model number MVLP-500) manufactured by Meiki Seisakusho was used for 20 seconds at a laminating pressure of 0.4 MPa. The laminate was heated and pressed at a pressing pressure of 0.8 MPa for 20 seconds and at a laminating and pressing temperature of 90 ° C. After cooling at room temperature, the polyethylene terephthalate film was peeled off. Thus, the laminated body by which the molded object was laminated | stacked on the uneven substrate was obtained.

  In the obtained laminate, the degree of the depression on the upper surface of the molded part corresponding to the part where there is no copper pattern between the copper patterns of the concave and convex board, with the molded part corresponding to the part with the copper pattern of the concave and convex board as a standard. It was measured. The unevenness was measured with a surface roughness meter (trade name “SJ-301”, manufactured by Mitutoyo Corporation).

  The total number of places where there are no dents and 25 places where the depth of the dent on the center line between the copper patterns is within 1 μm among the 25 parts of the molded body corresponding to the part where there is no copper pattern on the uneven substrate T2 was counted, and embedding property 2 was determined according to the following criteria. The larger the total number T2, the better the embedding with respect to the unevenness.

[Evaluation criteria for embedding 2]
A: Total number T2 is 25
B: Total number T2 is 23-24
C: Total number T2 is 20-22
D: Total number T2 is 0 to 19

(3) Embeddability 3
A copper-clad laminate (a laminate of a 150 μm thick glass epoxy substrate and a 35 μm thick copper foil) was prepared. The copper foil was etched to produce 26 copper patterns having an L / S of 50 μm / 50 μm and a length of 1 cm to obtain an uneven substrate.

  The molded bodies (thickness: 50 μm) obtained in the examples and comparative examples were stacked with the concavo-convex substrate, and a vacuum pressurization laminator machine (model number MVLP-500) manufactured by Meiki Seisakusho was used for 20 seconds at a laminating pressure of 0.4 MPa. The laminate was heated and pressed at a pressing pressure of 0.8 MPa for 20 seconds and at a laminating and pressing temperature of 90 ° C. After cooling at room temperature, the polyethylene terephthalate film was peeled off. Thus, the laminated body by which the molded object was laminated | stacked on the uneven substrate was obtained.

  In the obtained laminate, the degree of the depression on the upper surface of the molded part corresponding to the part where there is no copper pattern between the copper patterns of the concave and convex board, with the molded part corresponding to the part with the copper pattern of the concave and convex board as a standard. It was measured. The unevenness was measured with a surface roughness meter (trade name “SJ-301”, manufactured by Mitutoyo Corporation).

  The total number of places where there are no dents and 25 places where the depth of the dent on the center line between the copper patterns is within 1 μm among the 25 parts of the molded body corresponding to the part where there is no copper pattern on the uneven substrate T3 was counted and embedding property 3 was determined according to the following criteria. The larger the total number T3, the better the embedding with respect to the unevenness.

[Criteria for Embedding 3]
A: Total number T3 is 25
B: Total number T3 is 23-24
C: Total number T3 is 20-22
D: Total number T3 is 0 to 19

(4) Storage stability Using a viscoelasticity measuring apparatus ("AR2000ex" manufactured by TA Instruments Japan Co., Ltd.), the viscosity η * at 80 ° C of the molded article immediately after it was obtained was measured.

  Next, the molded body was left at 24 ° C. for 3 days. The viscosity η * at 80 ° C. of the molded product after standing was measured.

  From the measured value of the obtained viscosity η *, the storage stability was determined according to the following criteria.

[Criteria for storage stability]
A: Change in viscosity η * of the molded body after standing is 5% or less with respect to the viscosity η * of the molded body immediately after being obtained. B: Standing with respect to the viscosity η * of the molded body immediately after being obtained. The change in the viscosity η * of the molded body after that exceeds 5%

  The results are shown in Table 1 below.

(Examples 13 and 14)
In Examples 13 and 14, DMAP (N, N-dimethyl-4-aminopyridine, manufactured by Wako Pure Chemical Industries, Ltd.) was used as the curing accelerator instead of the imidazole compound.

  A resin composition and a molded body were obtained in the same manner as in Example 1 except that the type and blending amount of the materials used were changed as shown in Table 2 below.

(Examples 15 to 18)
A resin composition and a molded body were obtained in the same manner as in Example 1 except that the type and blending amount of the materials used were changed as shown in Table 3 below.

(Evaluation)
Using the molded bodies obtained in Examples 13 to 18, the evaluation items (1) Embeddability 1, (2) Embeddability 2, Embeddability 3 and (4) Storage stability were evaluated. did. Furthermore, the arithmetic average roughness Ra of the following (5) was also evaluated for the molded bodies obtained in Examples 13 to 18, Examples 6 and 7, and Comparative Examples 3 and 4. Further, the molded bodies obtained in Example 1 and Examples 15 to 18 were also evaluated for the following (6) breaking strength.

(5) Arithmetic average roughness Ra (surface roughness)
[Preparation of uncured resin sheet]
A release-treated transparent polyethylene terephthalate (PET) film (trade name “PET5011 550”, thickness 50 μm, manufactured by Lintec Corporation) was prepared. Using the applicator on this PET film, the obtained resin compositions of Examples and Comparative Examples were applied so that the thickness after drying was 50 μm. Next, it was dried in a gear oven at 100 ° C. for 12 minutes to prepare an uncured product of a resin sheet having an area of 200 mm × 200 mm and a thickness of 50 μm. A laminate A and a semi-cured body A2 having the following semi-cured bodies A1 were produced using the uncured product of the produced resin sheet.

[Preparation of laminate A having semi-cured product A1]
A circuit board was prepared on a glass epoxy substrate having a copper thickness of 25 μm, a pattern length of 3 cm, and 10 patterns of L / S = 75 μm / 75 μm. An uncured product of the obtained resin sheet was vacuum laminated on the circuit board. At the time of vacuum lamination, lamination was performed using a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.) under lamination conditions of 90 ° C., 0.6 MPa, vacuum 40 seconds, and pressure 40 seconds. It should be noted that lamination was performed under the same conditions when vacuum laminating described later. Thereafter, the uncured product of the resin sheet was precured at 150 ° C. for 1 hour to obtain a laminate A composed of a semi-cured product A1 and a circuit board obtained by semi-curing the uncured product of the resin sheet.

  Thereafter, the surface of the semi-cured body A1 of the obtained laminate A was subjected to the following (a) swelling treatment, and then the following (b) permanganate treatment, that is, roughening treatment.

(A) Swelling treatment:
The obtained laminate A was placed in a swelling liquid at 80 ° C. (Swelling Dip Securigant P, manufactured by Atotech Japan) and rocked for 10 minutes. Thereafter, it was washed with pure water.

(B) Permanganate treatment (roughening treatment):
The swelled laminate A was placed in a 80 ° C. potassium permanganate (concentrate compact CP, manufactured by Atotech Japan) roughened aqueous solution and rocked for 10 minutes. Then, it wash | cleaned for 2 minutes with the washing | cleaning liquid (Reduction securigant P, the Atotech Japan company make) of 25 degreeC, and also wash | cleaned further with the pure water. A semi-cured product A2 having a roughened surface was obtained.

[Measurement of arithmetic average roughness Ra]
Using the non-contact type surface roughness meter (trade name “WYKO”, manufactured by Beiko), the semi-cured body A1 whose surface is not roughened and the semi-cured body A2 whose surface is roughened The arithmetic average roughness Ra of each surface was measured. Arithmetic mean roughness Ra conformed to JIS B 0601-1994.

(6) Breaking strength After a 50 μm thick sheet-like molded body on a PET film was cured in a gear oven at 180 ° C. for 3 hours, the PET film was peeled off to obtain a cured body having a thickness of 50 μm. The cured body was cut into a length of 100 mm and a width of 10 mm and processed into a strip-shaped test piece.

  Using a tensile tester (Shimadzu Corporation: AGSJ-100), the breaking strength of the test piece was measured in accordance with the test method of JIS K7161 and the test conditions of JIS K7127.

  The results are shown in Tables 2-3 below.

  In addition, even when the semi-cured body A1 and the semi-cured body A2 are produced using a molded body obtained by molding the resin composition into a sheet shape instead of the resin composition, the arithmetic average roughness in Examples and Comparative Examples The same tendency was observed for the size of Ra.

Claims (11)

Epoxy resin,
An active ester compound;
A first silica having an average particle size of 0.1 μm or more and 10 μm or less;
A second silica having an average particle diameter of 1 nm or more and less than 100 nm,
The resin composition whose content of the said 2nd silica with respect to 100 weight part of said 1st silicas is 0.6-30 weight part. In 100% by weight of the resin composition (excluding the solvent when the resin composition contains a solvent), the total content of the first and second silicas is 25 to 80% by weight,
2. The resin composition according to claim 1, wherein the content of the second silica is 0.45 to 24.5 parts by weight with respect to 100 parts by weight of the total resin components contained in the resin composition.   The total content of the first and second silicas is 45 to 75% by weight in 100% by weight of the resin composition (excluding the solvent when the resin composition includes a solvent). Resin composition.   The resin composition of Claim 2 or 3 whose content of a said 2nd silica is 4-18 weight part with respect to a total of 100 weight part of the resin component contained in the resin composition.   The resin composition according to any one of claims 1 to 4, wherein a content of the second silica is 0.8 to 30 parts by weight with respect to 100 parts by weight of the first silica.   The resin composition according to claim 5, wherein the content of the second silica is 2 to 15 parts by weight with respect to 100 parts by weight of the first silica.   The resin composition according to claim 5, wherein the content of the second silica is 3 to 15 parts by weight with respect to 100 parts by weight of the first silica.   The resin composition according to any one of claims 1 to 7, wherein the first and second silicas are treated with a silane coupling agent.   The resin composition according to claim 8, wherein at least one of the first and second silicas is treated with an epoxy silane coupling agent.   The molded object in which the resin composition of any one of Claims 1-9 was shape | molded by the sheet form.   The molded object according to claim 10, which has a thickness of 5 to 100 µm.