JP2012062422A - Resin composition and molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of obtaining a molded body having high performance fitting to unevenness and high surface smoothness when laminated on a member having holes or unevenness on the surface thereof, and to provide the molded body.SOLUTION: The resin composition includes an epoxy resin, a phenolic curing agent, a first silica having an average particle size of 0.1-10 μm, and a second silica having that of 1-100 nm. The content of the second silica is 0.6-30 pts.wt. based on 100 pts.wt. of the first silica. The molded body is produced by molding the resin composition in a sheet-like form.

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, Patent Document 1 below discloses a resin composition containing a cyanate resin, a phenol resin, and an inorganic filler. Here, it is described that the resin composition has high flame retardancy and heat resistance and a low coefficient of linear expansion. Furthermore, Patent Document 1 describes that it is preferable to use an epoxy resin in order to improve the reactivity of the cyanate resin.

  Patent Document 2 below discloses a resin composition containing a high molecular weight component having a weight average molecular weight of 100,000 to 600,000, a polyfunctional epoxy resin having a molecular weight of 500 or more, a phenol resin, and a filler. . Here, it is described that since the fluidity before curing is good, the resin composition can be sufficiently embedded in unevenness such as a wiring board and high adhesive strength is exhibited after curing. Furthermore, Patent Document 2 describes that when two or more kinds of fillers having different average particle diameters are included as the filler, the melt viscosity is lowered and excellent adhesive strength can be obtained after curing.

JP 2003-096296 A JP 2008-133456 A

  In the resin compositions described in Patent Documents 1 and 2, when the resin composition is applied onto a substrate having holes or irregularities on the surface, the hole filling property or irregularity followability is low, and the upper surface of the resin composition Smoothness may be low. Furthermore, even if the resin composition described in Patent Documents 1 and 2 is molded into a sheet shape to obtain a molded body, the obtained molded body has low filling property or uneven follow-up property, and the resin composition The smoothness of the top surface may be low.

  An object of the present invention is to provide a resin composition that can provide a molded article that has high unevenness followability and can improve surface smoothness when laminated on a member having a hole or unevenness on the surface, In addition, a molded body using the resin composition is provided.

  According to a wide aspect of the present invention, an epoxy resin, a phenol curing agent, a first silica having an average particle diameter of 0.1 μm or more and 10 μm or less, and a second silica having an average particle diameter 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 another specific aspect of the resin composition according to the present invention, the content of the second silica is 1 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, a vinyl silane coupling agent, or an amino silane coupling agent.

  The phenol curing agent is preferably a phenol curing agent represented by the following formula (1).

  In the above formula (1), m and n are each an integer of 1 or more.

  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, a phenol curing agent, 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 laminated | stacked on the member which has a hole or an unevenness | corrugation on the surface, uneven | corrugated followable | trackability is high, and A sheet-like molded body that can improve the smoothness of the surface 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, a phenol curing agent, a first silica having an average particle diameter of 0.1 μm or more and 10 μm or less, and a second silica having an average particle diameter 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 2 parts by weight, the still more preferred lower limit is 2.5 parts by weight, and the preferred upper limit is 25 parts by weight. A more preferred upper limit is 20 parts by weight, a still more preferred upper limit is 15 parts by weight, and a most preferred upper limit is 10 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 upper limit of the content of the second silica is 24.5 parts by weight with respect to 100 parts by weight of the total resin components contained in the resin composition.

  In addition, the said resin component contains an epoxy resin and a phenol hardening | curing agent, 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 said 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 a phenol curing agent (phenol compound). By using the phenol curing agent in combination with an epoxy resin and the first and second silica, when laminated on a member having holes or irregularities on the surface, the irregularity followability is high and the surface smoothness is enhanced. The sheet-like molded object which can be obtained can be obtained. Furthermore, by using a phenol curing agent, the glass transition temperature of the cured product can be increased, and the adhesion between the cured product and the metal layer can be further enhanced. The phenol curing agent has a phenolic hydroxyl group. Only one type of phenol curing agent may be used, or two or more types may be used in combination.

  Examples of the phenol curing agent include novolak type phenol, biphenol type phenol, naphthalene type phenol, dicyclopentadiene type phenol, aralkyl type phenol and dicyclopentadiene type phenol.

  Examples of commercially available phenol curing agents include phenolic compounds having an aminotriazine skeleton (“LA1356” and “LA3018-50P” manufactured by DIC).

  From the viewpoint of increasing the curability of the resin composition and the molded body and further reducing the surface roughness of the roughened or swollen cured product, the phenol compound is a novolak-type phenol compound or a triazine skeleton. It is preferable that it is a phenol compound which has this.

  The phenol compound is preferably a phenol curing agent represented by the following formula (1). By using this phenol curing agent, it is possible to obtain a sheet-like molded body that has higher unevenness followability and can further improve the surface smoothness.

  In the above formula (1), m and n are each an integer of 1 or more. m is preferably 100 or less, more preferably 50 or less. When m is less than or equal to the above upper limit, the viscosity of the resin composition is lowered, so that the unevenness followability is further enhanced. From the viewpoint of versatility, n is preferably 10 or less, more preferably 3 or less.

  From the viewpoint of increasing the curability of the resin composition and further reducing the surface roughness of the surface of the roughened or swollen cured product, the hydroxyl equivalent of the phenol compound is 500 or less, more preferably 220 or less. It is. From the viewpoint of further increasing the glass transition temperature of the cured product, the hydroxyl equivalent of the phenol compound is more preferably 180 or less. The hydroxyl group equivalent represents a phenolic hydroxyl group equivalent.

  The compounding ratio of the epoxy resin and the curing agent is not particularly limited. The compounding ratio of the epoxy resin and the curing agent is appropriately determined depending on the types of the epoxy resin and the curing agent.

[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. 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.

  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 phenol curing agent. 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.

  The resin composition according to the present invention may contain a curing accelerator other than the imidazole compound. As for said other hardening accelerator, only 1 type may be used 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 a phenol curing agent, 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 epoxy silane, phenyl silane, amino silane, and imidazole silane. From the viewpoint of further enhancing the dispersibility of the first and second silica in the resin composition, at least one of the first and second silicas is an epoxy silane coupling agent, a vinyl silane coupling agent, or an aminosilane cup. It is preferably treated with a ring agent. At least one of the first and second silicas is preferably treated with an epoxy silane coupling agent, preferably treated with a vinyl silane coupling agent, and further treated with an amino silane coupling agent. It is also preferable.

  From the viewpoint of further enhancing the dispersibility of the first and second silica in the resin composition, the first silica is treated with an epoxy silane coupling agent, a vinyl silane coupling agent, or an amino silane coupling agent. preferable. The first silica is preferably treated with an epoxy silane coupling agent, preferably treated with a vinyl silane coupling agent, and further preferably treated with an amino silane coupling agent.

  From the viewpoint of further enhancing the dispersibility of the first and second silica in the resin composition, the first and second silicas are each treated with an epoxy silane coupling agent, a vinyl silane coupling agent, or an amino silane coupling agent. It is preferable that Each of the first and second silicas is preferably treated with an epoxy silane coupling agent, preferably treated with a vinyl silane coupling agent, and further treated with an amino silane coupling agent. preferable.

  The said epoxy silane coupling agent is a silane coupling agent which has an epoxy group, for example, is an epoxy silane. The vinyl silane coupling agent is a silane coupling agent having a vinyl group, for example, vinyl silane. The aminosilane coupling agent is a silane coupling agent having an amino group, for example, aminosilane.

  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. The above “100 wt% resin composition (excluding the solvent when the resin composition contains a solvent)” means 100 wt% resin composition when the resin composition does not contain a solvent. When the solvent contains a solvent, it represents 100% by weight in total of the components excluding the solvent in the resin composition.

(Other ingredients)
The resin composition according to the present invention preferably contains a high molecular weight component having a weight average molecular weight of 5000 or more. By using the high molecular weight component, when the surface of the cured product after the curing is roughened, the surface roughness of the roughened surface can be reduced, and the adhesive strength between the cured product and the metal layer is reduced. Can be high. Furthermore, the thickness of the B stage film or the cured product layer can be made uniform by the high molecular weight component. As for the said high molecular weight component, only 1 type may be used and 2 or more types may be used together.

  Examples of the high molecular weight component include phenoxy resin, polyvinyl acetal resin, rubber component, and organic filler.

  The high molecular weight component preferably includes at least one of a polyvinyl acetal resin and a phenoxy resin, and more preferably at least one of a polyvinyl acetal resin and a phenoxy resin. By using the polyvinyl acetal resin or the phenoxy resin, the thickness of the B stage film or the cured product layer can be made more uniform. When the resin composition according to the present invention includes a phenoxy resin, only one kind of the phenoxy resin may be used, or two or more kinds may be used in combination. A conventionally known phenoxy resin can be used as the phenoxy resin.

  Examples of the phenoxy resin include phenoxy resins having a skeleton such as a bisphenol S skeleton, a bisphenol A skeleton, a bisphenol F skeleton, a phenol skeleton, a biphenol skeleton, or a naphthalene skeleton. The weight average molecular weight of the phenoxy resin is preferably 5000 or more, and preferably 300,000 or less.

  Commercially available products of the above phenoxy resins include “YP50”, “YP55” and “YP70” manufactured by Toto Kasei Co., Ltd., and “1256B40”, “4250”, “4256H40”, “4275”, “4275” manufactured by Japan Epoxy Resin Co., Ltd. YX6954BH30 "and" YX8100BH3 ".

  When the resin composition according to the present invention includes a polyvinyl acetal resin, only one kind of the polyvinyl acetal resin may be used, or two or more kinds may be used in combination. A conventionally known polyvinyl acetal resin can be used as the polyvinyl acetal resin. The polyvinyl acetal resin is preferably a polyvinyl butyral resin.

  As a commercial item of the said polyvinyl acetal resin, the ESREC BL series, the ESREC BX series, the ESREC BM series, the ESREC BH series, the ESREC KS series (all are made by Sekisui Chemical Co., Ltd.), etc. are mentioned.

  When the resin composition according to the present invention includes a rubber component, only one rubber component may be used, or two or more rubber components may be used in combination. As the rubber component, a conventionally known rubber component can be used. Examples of the rubber component include acrylic rubber, nitrile rubber, isoprene rubber, urethane rubber, chloroprene rubber, silicone rubber, and styrene-butadiene rubber.

  Examples of commercially available rubber components include Tuftec H series, Tuftec M series, and Tuftec P series (all of which are manufactured by Asahi Kasei Corporation).

  The weight average molecular weight of the high molecular weight component is preferably 5000 or more, more preferably 10,000 or more. The upper limit of the weight average molecular weight of the high molecular weight component is not particularly limited. The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC).

  In 100% by weight of the resin composition (excluding the solvent when the resin composition contains a solvent), the content of the high molecular weight component is preferably 0.4% by weight or more, more preferably 0.7% by weight or more. , Preferably 5% by weight or less, more preferably 2.5% by weight or less. When the content of the high molecular weight component is not less than the lower limit, the thicknesses of the molded product and the cured product can be made more uniform. For example, the film forming property at the time of casting of a resin composition can be improved. When the content of the high molecular weight component is not more than the above upper limit value, the coefficient of thermal expansion of the cured product can be lowered, and the strain amount of the cured product can be reduced. Furthermore, when the content of the high molecular weight component is not more than the above upper limit value, fine irregularities can be formed on the surface of the cured product by the roughening treatment, and the adhesive strength between the cured product and the metal layer can be further increased. it can. In addition, the said high molecular weight component is a component which influences greatly the uniformity of the thickness of a molded object and hardened | cured material. Moreover, there exists a tendency for the adhesive strength of hardened | cured material and a metal layer to become low, so that there is much content of the said high molecular weight component.

  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, the said epoxy resin, and a high molecular weight component.

  Other resins include polyphenylene ether resin, phenoxy resin, polyacetal resin, divinyl benzyl ether resin, polyarylate resin, diallyl phthalate resin, polyimide resin, benzoxazine resin, benzoxazole resin, bismaleimide resin, cyanate resin and acrylate resin. Etc.

  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. It is preferable that the cured product is 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, “jER154” manufactured by Mitsubishi Chemical Corporation)
Epoxy resin (bisphenol A type epoxy resin, “RE-410S” manufactured by Nippon Kayaku Co., Ltd.)

(Curing agent)
Phenol curing agent (Maywa Kasei “MEH7800”, corresponding to the phenol curing agent represented by the above formula (1))
Phenol curing agent (“MEH7851-H” manufactured by Meiwa Kasei Co., Ltd.)

(Curing accelerator)
Imidazole compound (2-phenyl-4-methylimidazole, “2P4MZ” manufactured by Shikoku Chemicals)

(High molecular weight component)
High molecular weight component (modified biphenol skeleton-containing phenoxy resin solution, manufactured by Japan Epoxy Resin, trade name “YX6954BH30”, solid content 30% by weight, solvent is a mixed solvent of MEK (methyl ethyl ketone) and cyclohexanone)

(Silica component)
First silica-containing slurry A (epoxysilane treatment):
First silica (Silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm) is epoxy silane (3-glycidoxypropyltrimethoxysilane, “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.)) The first silica-containing slurry B (vinyl silane treatment) containing the first silica-containing slurry B) (surface-treated with 1.5 parts by weight of epoxysilane with respect to 100% by weight of silica):
The first silica (silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle diameter of 0.5 μm) is converted into 100% by weight of silica by vinylsilane (vinyltrimethoxysilane, “KBM-1003” manufactured by Shin-Etsu Chemical Co., Ltd.). First silica-containing slurry containing 1.5 parts by weight of vinyl silane with respect to the first silica-containing slurry C (aminosilane treatment):
The first silica (silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm) is aminosilane (N-phenyl-3-aminopropyltrimethoxysilane, “KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.). ), The first silica-containing slurry D (untreated) containing 100% by weight of silica and surface-treated with 1.5 parts by weight of aminosilane):
First silica-containing slurry containing silica (silica (“Ad-Tex” “SO-C2”, average particle size 0.5 μm)) Second silica-containing slurry P (epoxysilane treatment):
The second silica (silica (“Admanano” manufactured by Admatechs Co., Ltd., average particle diameter 10 nm) is changed to silica 100 by epoxysilane (3-glycidoxypropyltrimethoxysilane, “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.). Second silica-containing slurry containing 1.5% by weight of epoxysilane with respect to% by weight) Second silica-containing slurry Q (vinylsilane treatment):
The second silica (silica (“Admanano” manufactured by Admatechs Co., Ltd., average particle size 10 nm) is vinylsilane based on 100% by weight of silica by vinylsilane (vinyltrimethoxysilane, “KBM-1003” manufactured by Shin-Etsu Chemical Co., Ltd.)). Second silica-containing slurry containing 1.5 parts by weight of the surface-treated slurry. Second silica-containing slurry R (aminosilane treatment):
The second silica (silica (“Admanano” manufactured by Admatechs Co., Ltd., average particle diameter 10 nm) is converted into silica by aminosilane (N-phenyl-3-aminopropyltrimethoxysilane, “KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.)). Second silica-containing slurry containing 100% by weight of a surface-treated silica with 1.5 parts by weight of aminosilane. Second silica-containing slurry S (untreated):
Second silica-containing slurry containing second silica (silica (“Admanano” manufactured by Admatechs, average particle size 10 nm))

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

Example 1
To 50 parts by weight of methyl ethyl ketone, 25.00 parts by weight of an epoxy resin (phenol novolac-type epoxy resin, “jER154” manufactured by Japan Epoxy Resin Co., Ltd.) and a modified biphenol skeleton-containing phenoxy resin (trade name “YX6954BH30” manufactured by Japan Epoxy Resin Co., Ltd.) Add 4.5 parts by weight of solid, 47.50 parts by weight of first silica-containing slurry A and 2.50 parts by weight of second silica-containing slurry P, and add stirrer For 1 hour at 1200 rpm.

  Next, 20.00 parts by weight of a phenol curing agent (“MEH7800” manufactured by Meiwa Kasei Co., Ltd.) was further added, and the mixture was stirred at 1200 rpm for 90 minutes using a stirrer.

  Thereafter, 0.50 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 to 13 and Comparative Examples 1 to 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) 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 5% is more than 5% and 10% or less. C: The change in the viscosity η * of the molded body after being left is 10% with respect to the viscosity η * of the molded body immediately after being obtained. Over

(4) 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 a non-contact type surface roughness meter (trade name “WYKO”, manufactured by Beiko Co., Ltd.), the arithmetic average roughness Ra of the surface of the semi-cured product A2 whose surface was roughened was measured. Arithmetic mean roughness Ra conformed to JIS B 0601-1994.

  The results are shown in Table 1 below. In Table 1 below, the blending amount of the high molecular weight component indicates the blending amount of the modified biphenol skeleton-containing phenoxy resin that is a solid content, and the blending amount of the silica component is the solid content in the first and second silicas. The blending amount is shown. In Table 1 below, the types of the first silica-containing slurries A, B, C and D are abbreviated as A, B, C and D, and the types of the second silica-containing slurries P, Q, R and S are described. Was abbreviated as P, Q, R and S.

  In addition, even when the semi-cured body A2 is produced using a molded body obtained by molding the resin composition into a sheet shape instead of the resin composition, the arithmetic average roughness Ra in Examples and Comparative Examples A similar trend was seen.

Claims (9)

Epoxy resin,
A phenolic curing agent,
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 according to any one of claims 1 to 3, wherein a content of the second silica is 1 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 4, wherein the first and second silicas are treated with a silane coupling agent.   The resin composition according to claim 5, wherein at least one of the first and second silicas is treated with an epoxy silane coupling agent, a vinyl silane coupling agent, or an amino silane coupling agent. The resin composition according to any one of claims 1 to 6, wherein the phenol curing agent is a phenol curing agent represented by the following formula (1).

In the formula (1), m and n are each an integer of 1 or more.   The molded object in which the resin composition of any one of Claims 1-7 was shape | molded in the sheet form.   The molded object of Claim 8 whose thickness is 5-100 micrometers.