JP-7854758-B1 - Resin composition, laminate, coverlay film, adhesive sheet, resin-coated metal foil, metal-clad laminate, printed circuit board, semiconductor device, and method for manufacturing resin composition

JP7854758B1JP 7854758 B1JP7854758 B1JP 7854758B1JP-7854758-B1

Abstract

[Problem] To provide a resin composition that stably exhibits a sufficiently high relative permittivity and a sufficiently low dielectric loss tangent in the millimeter-wave band, and has minimal thickness change before and after the curing process by heating and pressing. [Solution] A resin composition containing a reactive polymer and a filler, wherein the relative permittivity at 10 GHz when the adhesive layer made of the resin composition is completely cured is 5.0 or more, the dielectric loss tangent at 10 GHz is 0.01 or less, the difference between the maximum and minimum values selected from a plurality of relative permittivity measurements in the range of 10 GHz to 80 GHz is 1.0 or less, the difference between the maximum and minimum values selected from a plurality of dielectric loss tangent measurements in the range of 10 GHz to 80 GHz is 0.004 or less, and the rate of change in the thickness of the adhesive layer, determined based on the thickness of the adhesive layer made of the resin composition before curing by heat pressing and the thickness after the adhesive layer is completely cured, is 36% or less. [Selection Diagram] None

Inventors

安藤秀樹
並木瑠玖
白岩寛之

Assignees

ニッカン工業株式会社

Dates

Publication Date: 20260507
Application Date: 20251001

Claims (8)

A resin composition containing a reactive polymer, an epoxy compound, and a filler , and dispersed by bead milling . The adhesive layer made of the resin composition has a relative permittivity of 5.0 or more at 10 GHz when fully cured, and a dielectric loss tangent of 0.01 or less at 10 GHz. The difference between the maximum and minimum values of the relative permittivity selected from among several relative permittivity measurements taken in the range of 10 GHz to 80 GHz is 1.0 or less. The difference between the maximum and minimum values of the dielectric loss tangent selected from among several dielectric loss tangents measured in the range of 10 GHz to 80 GHz is 0.004 or less. The rate of change in the thickness of the adhesive layer, which is determined based on the thickness of the adhesive layer made of the resin composition before curing by heat pressing and the thickness of the adhesive layer after it has been completely cured, is 36% or less. The reactive polymer is either a maleic acid-modified styrene-ethylene-butylene-styrene block copolymer or an acid-modified polypropylene resin. The acid-modified polypropylene resin satisfies the following conditions: weight-average molecular weight of 35,000, glass transition temperature of 20°C, and acid value of 12.5 mg KOH/g. The filler is strontium titanate or calcium titanate. A resin composition in which the average primary particle size of the filler is 0.1 μm or more and less than 1.0 μm .
The resin composition according to claim 1, wherein the content of the filler is 50 parts by mass or more per 100 parts by mass of the solid content of the resin composition.
The resin composition according to claim 1, wherein the content of the epoxy compound is 1 part by mass or more and 30 parts by mass or less per 100 parts by mass of the organic component contained in the resin composition, and where the organic component is the component of the solid content of the resin composition excluding the filler.
A laminate comprising an adhesive layer formed from the resin composition described in claim 1, and a substrate in contact with at least one surface of the adhesive layer, A laminate in which the substrate is formed from one or more materials selected from the group consisting of resin, release resin, paper, release paper, and metal.
A coverlay film, adhesive sheet, resin-coated metal foil, or metal-clad laminate comprising the laminate described in claim 4 .
A printed circuit board comprising the laminate described in claim 4 , or the coverlay film, adhesive sheet, resin-coated metal foil, or metal-clad laminate described in claim 5 .
A semiconductor device comprising a printed circuit board as described in claim 6 .
A resin composition containing a reactive polymer, an epoxy compound, and a filler. , The adhesive layer made of the resin composition has a relative permittivity of 5.0 or more at 10 GHz when fully cured, and a dielectric loss tangent of 0.01 or less at 10 GHz. The difference between the maximum and minimum values of the relative permittivity selected from among several relative permittivity measurements taken in the range of 10 GHz to 80 GHz is 1.0 or less. The difference between the maximum and minimum values of the dielectric loss tangent selected from among several dielectric loss tangents measured in the range of 10 GHz to 80 GHz is 0.004 or less. A method for producing a resin composition in which the rate of change in the thickness of the adhesive layer, determined based on the thickness of the adhesive layer made of the resin composition before curing by heat pressing and the thickness after the adhesive layer has been completely cured, is 36% or less, The reactive polymer is either a maleic acid-modified styrene-ethylene-butylene-styrene block copolymer or an acid-modified polypropylene resin. The acid-modified polypropylene resin satisfies the following conditions: weight-average molecular weight of 35,000, glass transition temperature of 20°C, and acid value of 12.5 mg KOH/g. The filler is strontium titanate or calcium titanate. The average primary particle size of the filler is 0.1 μm or more and less than 1.0 μm. A mixing step of mixing the reactive polymer, the filler, and the epoxy compound , A method for producing a resin composition, comprising a kneading step of kneading the mixture obtained in the mixing step using a bead mill .

Description

This invention relates to resin compositions, laminates, coverlay films, adhesive sheets, resin-coated metal foils, metal-clad laminates, printed circuit boards, semiconductor devices, and methods for producing resin compositions. In recent years, with the miniaturization and increased functionality of electronic components, higher density mounting is required on circuit boards. Similarly, there is a demand for smaller, thinner, and higher-density mounted components. In response to these demands, the use of high-dielectric-constant insulating layers in component-embedded substrates and the shortening of antenna circuits are attracting attention. As an example of such a high dielectric constant insulating layer, there are known examples, such as those highly filled with inorganic oxides having a high relative dielectric constant as fillers, as shown in Patent Documents 1 and 2. Japanese Patent Publication No. 2001-192536Japanese Patent Publication No. 2004-035858 The following describes specific examples of the resin composition, laminate, coverlay film, adhesive sheet, resin-coated metal foil, metal-clad laminate, printed circuit board, and semiconductor device according to the present invention. However, the present invention is not limited to these examples, and various modifications and combinations are possible without altering the spirit of the invention. 1. Resin Composition The resin composition according to this embodiment contains a reactive polymer and a filler. The components of the resin composition will be described below. In this embodiment, the resin composition includes a slurry obtained by dissolving or suspending the above-mentioned components in a solvent such as an organic solvent, or the slurry in a state obtained by applying this slurry to a substrate such as release paper and drying it (before heating), or the state after heating (partially cured or completely cured). <Reactive polymers> In this embodiment, the reactive polymer can be any type without particular limitations, as long as it does not significantly impair the required performance of the resin composition containing the reactive polymer or the printed circuit board made using the resin composition. From the viewpoint of minimizing the dielectric loss tangent of the resin composition, it is preferable to use a reactive polymer with a low dielectric loss tangent. Specifically, it is preferable that the dielectric loss tangent of the reactive polymer alone in a wide frequency band from 10 GHz to 80 GHz is 0.008 or less, more preferably 0.005 or less, even more preferably 0.003 or less, and particularly preferably 0.002 or less. Examples of reactive polymers as described above include resins having organic functional groups. From the viewpoint of improving heat resistance, reactive polymers having two or more organic functional groups in their molecules are preferable. Specific examples of such reactive polymers include acrylic resins, phenoxy resins, polyamide resins, polyimide resins, polyester resins, polyphenylene oxide resins, polyurethane resins, polyacetal resins, polyolefin resins, styrene-based elastomers, and other thermoplastic elastomers. Among these, polyimide resins, polyester resins, polyolefin resins, and styrene-based elastomers are particularly preferred from the viewpoint of heat resistance and dielectric loss tangent, with polyimide resins, polyolefin resins, and styrene-based elastomers being even more preferred. Polyimide resins are resins having imide rings as repeating units in their resin skeleton. Polyimide resins can be produced by various known methods, for example, by a method that includes the steps of: reacting a group of monomers including aromatic tetracarboxylic anhydrides and diamines such as dimeramines with a polyaddition reaction preferably at a temperature of about 60 to 120°C, more preferably at about 80 to 100°C, for preferably about 0.1 to 2 hours, more preferably about 0.1 to 0.5 hours to obtain a polyaddition product; and then reacting the obtained polyaddition product with an imidation reaction, i.e., a dehydration ring-closing reaction, preferably at a temperature of about 80 to 250°C, more preferably at about 100 to 200°C, for preferably about 0.5 to 50 hours, more preferably about 1 to 20 hours. Various known reaction catalysts and dehydrating agents can be used in the imidation reaction step. As reaction catalysts, for example, aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline can be used. Furthermore, as dehydrating agents, for example, aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride can be used. The imide ring-closing ratio of the polyimide resin is not particularly limited. Here, the imide ring-closing ratio refers to the content of cyclic imide bonds in the polyimide resin, and can be measured