KR20190133787A - Resin composition, insulation layer for wiring board, and laminated body - Google Patents

Abstract

(식 중, n은 3 또는 4이다)
로 표현되는 인계 화합물 (C)와, 유기 충전제 또는 무기 충전제인 충전제 (D)를 포함한다.The resin composition which is excellent in flame retardancy, circuit embedding property, handling property (flexibility), etc., and which can bring about significantly low dielectric loss tangent is provided. This resin composition is predetermined high viscosity resin (A) whose viscosity in 120 degreeC is 8000 Pa.s or more, predetermined low viscosity resin (B) whose viscosity in 120 degreeC is less than 8000 Pa.s, and a following formula. :

(Wherein n is 3 or 4)
Phosphorus-containing compound (C) represented by the above, and filler (D) which is an organic filler or an inorganic filler.

Description

Resin composition, insulation layer for wiring board, and laminated body

The present invention relates to a resin composition, an insulating layer for a wiring board, and a laminate.

Printed wiring boards are widely used in electronic devices such as portable electronic devices. In particular, with high functionalization of portable electronic devices and the like in recent years, high frequency signals have been advanced, and printed wiring boards suitable for such high frequency applications are required. This high frequency printed wiring board is desired to have low transmission loss in order to enable transmission without degrading the quality of the high frequency signal. Although a printed wiring board is equipped with the copper foil processed by the wiring pattern, and the insulated resin base material, a transmission loss consists mainly of the conductor loss which originates in a copper foil, and the dielectric loss which originates in an insulated resin base material. Therefore, in copper foil with a resin layer applied to a high frequency use, it is preferable to suppress the dielectric loss resulting from a resin layer. For this purpose, the resin layer requires excellent dielectric properties, in particular low dielectric tangent.

The material for printed wiring boards also requires characteristics such as flame retardancy, heat resistance, peel strength with copper foil, and the like, and various resin compositions have been proposed to satisfy such demands. In particular, a resin having a low dielectric loss tangent tends to be inferior in flame retardancy, so that a flame retardant is preferably added to the resin composition. Although halogen-based compounds are known as such flame retardants, they are not environmentally preferable because of harmful substances such as dioxins generated during incineration. In addition, compounds of halogen (eg bromine, etc.) except fluorine have poor dielectric properties.

Then, the resin composition which contained the cyclophosphazene compound which is a halogen-free flame retardant is proposed. For example, Patent Document 1 (International Publication No. 2015/133292) discloses a cyclophosphazene compound containing (A) polyphenylene ether (PPE) having a number average molecular weight of 500 to 5000, (B) a vinyl group, ( C) A resin composition containing a non-halogen epoxy resin, (D) cyanate ester compound, and (E) filler is disclosed. According to this resin composition, a print excellent in flame retardancy, thermal expansion coefficient, and heat resistance during moisture absorption is disclosed. It is possible to provide a wiring board.

On the other hand, the resin composition containing cyano phenoxy modified phosphazene is known as a flame-retardant resin composition suitable as a soldering resist for flexible printed wiring boards. For example, Patent Document 2 (Japanese Patent Laid-Open No. 2009-191252) discloses (A) a carboxyl group and an ethylenically unsaturated group-containing urethane resin, (B) a phenoxy phosphazene compound, (C) a photopolymerization initiator, (D Disclosed is a flame retardant resin composition comprising an ethylenically unsaturated group-containing compound, (E) flame retardant component, (F) thermosetting component, and (G) thermosetting aid. In this document, the phenoxy phosphazene compound is merely positioned as a flame retardant having excellent compatibility with the urethane resin for soldering resists, and no studies on dielectric loss tangent have been made.

International Publication No. 2015/133292 Japanese Patent Publication No. 2009-191252

In printed wiring board manufacture, formation of the insulating layer on a circuit is performed by laminating | stacking copper foil with resin on the board | substrate with a circuit, and burying a circuit with the resin layer as an insulating layer. However, since this work is performed in the semi-cured state (B-stage), if the fluidity (resin flow) of the resin is too high, it is impossible to secure the necessary insulating layer thickness due to the outflow of the resin. If the fluidity (resin flow) of is too low, it will harden | cure undesired voids (voids) in the insulating layer. In other words, even if the resin flow is too high or too low, the circuit embedding property is lowered, so extremely careful compositional design based on the variation of these characteristics is desired. On the other hand, in the resin composition after hardening (C-stage), it is desired to be equipped with the performance of low dielectric loss tangent, excellent heat resistance, flame retardancy, handling property (flexibility), and the like. However, when attempting a composition design that focuses on improving the circuit embedability and handling property (flexibility), various properties of the resin composition after curing tend to be poor, and in particular, both flame retardancy and dielectric properties (low dielectric loss tangent) are difficult to achieve. . That is, the resin composition excellent also in the circuit embedding property in the semi-hardened state (B-stage) is desired, while improving the characteristics (dielectric properties, flame retardance, etc.) of the resin composition of a hardened state (C-stage).

MEANS TO SOLVE THE PROBLEM This invention is a flame retardance and circuit embedding property of the resin composition containing predetermined | prescribed high viscosity resin (A), predetermined low viscosity resin (B), predetermined phosphorus compound (C), and predetermined filler (D) this time. It has been found that excellent properties such as handling properties (flexibility) and a significant low dielectric loss are obtained.

Accordingly, an object of the present invention is to provide a resin composition that is excellent in various properties such as flame retardancy, circuit embedding, handling property (flexibility), and which can bring about a significantly low dielectric tangent.

According to one embodiment of the present invention,

Cyanate compound, polyarylene ether compound, cycloolefin compound, hydrogenated or non-hydrogenated styrene-based elastomer, polyimide compound, siloxane compound, polyalkyl compound, and epoxy having a viscosity at 120 ° C. or higher. At least one high viscosity resin (A) selected from the group consisting of compounds having a reaction mechanism that does not generate hydroxyl groups when reacting with the compound,

Cyanate compound, polyarylene ether compound, cycloolefin compound, hydrogenated or non-hydrogenated styrene-based elastomer, polyimide compound, siloxane compound, polyalkyl compound, and epoxy having a viscosity at 120 ° C. At least one low viscosity resin (B) selected from the group consisting of compounds having a reaction mechanism that does not generate hydroxyl groups when reacting with the compound,

Formula (I):

(Wherein n is 3 or 4)

Phosphorus-based compound (C) represented by

Fillers (D) which are organic or inorganic fillers

It is provided, a resin composition comprising a.

According to another embodiment of the present invention, an insulating layer for a wiring board formed by curing the resin composition is provided.

According to another aspect of the present invention, there is provided a laminate comprising a resin layer formed by curing the resin composition on the surface of a metal layer.

Resin composition

The resin composition of this invention contains a high viscosity resin (A), a low viscosity resin (B), a phosphorus compound (C), and a filler (D). High viscosity resin (A) is resin whose viscosity in 120 degreeC is 8000 Pa.s or more, A cyanate compound, a polyarylene ether compound, a cycloolefin compound, a hydrogenated or non-hydrogenated styrene elastomer, a polyimide compound, It is 1 or more types chosen from the group which consists of a compound which has a reaction mechanism which does not generate a hydroxyl group when reacting with a siloxane compound, a polyalkyl compound, and an epoxy compound. The low-viscosity resin (B) has a viscosity at 120 ° C. of less than 8000 Pa · s, a cyanate compound, a polyarylene ether compound, a cycloolefin compound, a hydrogenated or non-hydrogenated styrene elastomer, a polyimide compound, It is 1 or more types chosen from the group which consists of a compound which has a reaction mechanism which does not generate a hydroxyl group when reacting with a siloxane compound, a polyalkyl compound, and an epoxy compound. Phosphorus compound (C) is a cyclic cyanophenoxyphosphazene compound represented by Formula (I) mentioned above. Filler (D) is an organic filler or an inorganic filler. Thus, according to the resin composition containing predetermined high viscosity resin (A), predetermined low viscosity resin (B), predetermined phosphorus-based compound (C), and predetermined filler (D), circuit embedding property and handling property ( Flexibility), and after curing, significantly lower dielectric tangent and flame retardancy can be obtained. For example, in the resin composition of this invention, the dielectric loss tangent in 10 microseconds after hardening becomes like this. Preferably it is less than 0.0030, More preferably, it is less than 0.0025, More preferably, it is less than 0.0020. The lower limit of the dielectric tangent is not particularly limited, but is typically 0.0001 or more.

High Viscosity Resin (A) and Low Viscosity Resin (B)

The viscosity in 120 degreeC of the high viscosity resin (A) contained in the resin composition of this invention is 8000 Pa.s or more, Preferably it is 10000-30000 Pa.s, More preferably, it is 50000-20000 Pa.s, Especially Preferably it is 70000-150000 Pa.s. On the other hand, the viscosity in 120 degreeC of the low viscosity resin (B) contained in the resin composition of this invention is less than 8000 Pa.s, Preferably it is 5000 Pa.s or less, More preferably, it is 1000 Pa.s or less Especially preferably, it is 0.0001-10 Pa.s. By mixing two kinds of resins in this way, a preferable resin flow can be realized to improve the circuit embedding at the time of circuit formation, and also the handling property (flexibility) can be improved.

In addition, the "viscosity in 120 degreeC" referred to in this specification is JISK using a rheometer (dynamic viscoelasticity measuring apparatus) (HAAKE MARS by Thermo Scientific) with respect to a semi-hardened state (B-stage). Based on 7117, it measures by the following method. That is, 120 when the resin sample of diameter 10mm x thickness 100micrometer was installed between the plate of diameter 10mm and the plate of the torque measurement part of diameter 10mm, and it heated up at the angular velocity of 6.2832rad / s and the temperature increase rate of 2 degree-C / min. The viscosity in ° C was measured. The viscosity was measured 3 times and 3 average values were employ | adopted.

The high viscosity resin (A) and the low viscosity resin (B) are each independently a cyanate compound, a polyarylene ether compound, a cycloolefin compound, a hydrogenated or non-hydrogenated styrene-based elastomer, a polyimide compound, a siloxane compound, a poly It is selected from the group which consists of an alkyl compound and the compound which has a reaction mechanism which does not generate a hydroxyl group when reacting with an epoxy compound. These compounds, either by themselves (in the case of polymers) or when the curing agent is added and cured (in the case of monomers), all result in low dielectric properties (eg, dielectric tangents of 0.005 or less at 10 Gz).

According to a preferred embodiment of the present invention, the high viscosity resin (A) and / or the low viscosity resin (B) may contain a cyanate compound. In particular, it is more preferable that the low viscosity resin (B) contains a cyanate compound. In any case, the cyanate compound may be any organic compound containing a cyanate group or a triazine skeleton, and is not particularly limited. Although the functional number of the compound containing a cyanate group is not specifically limited whether it is monofunctional or polyfunctional, Multifunctional is easy to use for copper foil (RCC) with resin from a viewpoint of crosslinking hardening. As an example of the compound containing a cyanate group, a phenol novolak-type cyanate, cresol novolak-type cyanate, dicyclopentadiene novolak-type cyanate, biphenyl novolak-type cyanate, bisphenol A-type dicyanate, bisphenol F Type dicyanate, dicyclopentadiene dicyanate, biphenyl dicyanate, and the like. These cyanate compounds may be used by 1 type, and may use 2 or more types together. In addition, in the case of the cyanate compound containing a triazine skeleton, if the 1 type, or 2 or more types of compound of the cyanate compound containing a cyanate group contains the compound which trimerized, it will not specifically limit. Although the triazine frame | skeleton may or may not contain the reactive functional group, it is preferable to use for the copper foil with resin (RCC) provided with the resin from the viewpoint of crosslinking hardening.

According to a preferred embodiment of the present invention, the high viscosity resin (A) and / or the low viscosity resin (B) may comprise a polyarylene ether compound, preferably a polyphenylene ether compound. It is more preferable that especially low viscosity resin (B) contains a polyphenylene ether compound. In any case, the polyarylene ether compound to the polyphenylene ether compound may be represented by the following formula:

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, n is a repeating number and typically 4 to 1000)

It is preferable that it is a compound containing the skeleton represented by in a molecule | numerator. Examples of the polyphenylene ether compound used in the low viscosity resin (B) include styrene derivatives of polyphenylene ether oligomers, terminal hydroxyl-modified polyphenylene ether oligomers, terminal methacryl modified polyphenylene ether oligomers, and terminal glycidyl ethers. And modified polyphenylene ether oligomers. As a product example of the styrene derivative of a polyphenylene ether oligomer, OPE-2St-1200 and OPE-2St-2200 by Mitsubishi Gas Chemical Co., Ltd. are mentioned. Examples of the product of the terminal hydroxyl group-modified polyphenylene ether oligomer include SA-90 and SA-120 manufactured by SABIC. SA-9000 by SABIC Corporation is mentioned as a product example of terminal methacryl modified polyphenylene ether oligomer.

Especially preferably, the polyphenylene ether compound used for low viscosity resin (B) is a following formula:

(Wherein n is 1 to 30 and m is 1 to 30)

It contains the polyphenylene ether resin of the number average molecular weight less than 3000 represented by the more preferable number average molecular weights 800-2800. Examples of the product of the polyphenylene ether resin that satisfies the above formula include OPE-2St-1200 and OPE-2St-2200 manufactured by Mitsubishi Gas Chemical Co., Ltd. In addition, you may use the value measured by polystyrene conversion by GPC (gel permeation chromatography) method as a number average molecular weight.

According to a preferred embodiment of the present invention, the high viscosity resin (A) and / or the low viscosity resin (B) may contain a cycloolefin compound. A cycloolefin compound is a following formula:

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently —H or an alkyl group having 1 to 5 carbon atoms and n is 1 to 3000)

A compound containing a dicyclopentadiene skeleton represented by the formula, or the following formula:

(Wherein X is —CH ₂ — or —C ₂ H ₄ —, R ₁ , R ₂ , R ₃ and R ₄ are each independently —H or an alkyl group having 1 to 5 carbon atoms, n is 0 to 2 , m is from 1 to 1000)

A compound containing a norbornene skeleton represented by the formula, or the following formula:

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently —H or an alkyl group having 1 to 5 carbon atoms and n is 1 to 3000)

It is preferable that it is either of the compounds containing the indane skeleton represented by As an example of a cycloolefin compound, 1 or more types chosen from (i) dicyclopentadiene type | mold epoxy resin, (ii) norbornene monomer, (iii) the said dicyclopentadiene skeleton, the said norbornene skeleton, and the said indan skeleton Cycloolefin type polymer containing a skeleton, etc. are mentioned. As a product example of a cycloolefin type polymer, ZEONOR (registered trademark) by Nippon Xeon Corporation, TOPAS (registered trademark) by Topas Advanced Polymers GmbH, etc. are mentioned.

According to a preferred embodiment of the present invention, the high viscosity resin (A) and / or the low viscosity resin (B) may include a styrene elastomer. In particular, it is more preferable that the high viscosity resin (A) contains a styrene-based elastomer. In any case, the styrene-based elastomer may be either hydrogenated or non-hydrogenated. That is, a styrene-type elastomer is a compound containing the site | part derived from styrene, and is a polymer which may include the site | part derived from the compound which has a polymerizable unsaturated group, such as olefin, besides styrene. When a double bond exists in the site | part derived from the compound which has a unsaturated group which can superpose | polymerize a styrene-type elastomer, the double bond part may be hydrogenated and may not be hydrogenated. As an example of a styrene-type elastomer, TR made by JSR Corporation, SIS made by JSR Corporation, Taftech (registered trademark), Asahi Kasei Co., Ltd., Kurareze Septon (registered trademark), and Kurashike Corporation Bra (registered trademark), and the like. In particular, it is preferable to use hydrogenated styrene-butadiene elastomer as high viscosity resin (A).

According to a preferred embodiment of the present invention, the high viscosity resin (A) and / or the low viscosity resin (B) may contain a polyimide compound. The polyimide compound is a compound containing an imide skeleton, and the skeleton of the acid anhydride of the precursor and the amine may be any skeleton.

According to a preferred embodiment of the present invention, the high viscosity resin (A) and / or the low viscosity resin (B) may contain a siloxane compound. The siloxane compound is of the formula:

(Wherein R ₁ and R ₂ are each independently a siloxane skeleton branched into an alkyl group, a phenyl group or a side chain, n is from 1 to 100)

Although it is typical that it is a compound containing the siloxane skeleton represented by the thing, it is preferable to include skeleton or functional groups other than a siloxane from the point of compatibility or reactivity with other resin. Silicone oil etc. are mentioned as an example of a siloxane compound. For example, KF-8010, X-22-161A, X-22-2445 and Toray Dow Corning Co., Ltd. BY16-853U made from Shin-Etsu Chemical Co., Ltd. from the viewpoint of the reactivity and compatibility with other components. You may use the thing which modified | denatured arbitrarily the silicone oil which has reactive functional groups, such as BY16-855, and the thing prepolymerized.

According to a preferred embodiment of the present invention, the high viscosity resin (A) and / or the low viscosity resin (B) may contain a polyalkyl compound. The polyalkyl compound is represented by the following formula:

Wherein n is from 2 to 100000

Although it is typical that it is a compound containing the alkyl skeleton represented by, it is also possible to optionally include a skeleton other than the alkyl skeleton. Examples of the polyalkyl compound, there may be mentioned polyethylene, polypropylene, Mitsui Kagaku whether or sikki manufactured claim olefin copolymer of APEL ^TM, etc., long-chain alkyl, such as epoxy.

According to a preferred embodiment of the present invention, the high viscosity resin (A) and / or the low viscosity resin (B) may include a compound having a reaction mechanism that does not generate hydroxyl groups when reacting with the epoxy compound. It is more preferable that especially low viscosity resin (B) contains the said compound. In any case, examples of the compound include imidazole, active ester, carbodiimide and the like, and carbodiimide is particularly preferable from the viewpoint of reactivity.

As described above, the high viscosity resin (A) and the low viscosity resin (B) may be the same or different types of resin except for the viscosity, but hydrogenated or non-hydrogenated styrene elastomers are selected as the high viscosity resin (A), Moreover, it is especially preferable to select a polyarylene ether compound as low viscosity resin (B). And as a polyarylene ether compound, it is more preferable to select a polyphenylene ether compound.

Although the content rate of the various components of the resin composition of this invention can be optimized by the combination of each component, and content rate is not specifically limited, Content of a high viscosity resin (A) is high viscosity resin (A) and low viscosity resin. The total amount of (B) and the phosphorus compound (C) is preferably 10 to 80 parts by weight, more preferably 15 to 75 parts by weight, still more preferably 20 to 70 parts by weight, particularly preferably 25 to 65 parts by weight, most preferably 30 to 60 parts by weight. The content of the high viscosity resin (A) described above is particularly preferably suitable when the high viscosity resin (A) is a hydrogenated or non-hydrogenated styrene elastomer, and the low viscosity resin (B) is a polyphenylene ether compound.

On the other hand, content of the low-viscosity resin (B) in the resin composition of this invention makes the total amount of a high-viscosity resin (A), the low-viscosity resin (B), and a phosphorus compound (C) 10 weight part, 10-50 weight part It is preferable that it is denier, More preferably, it is 15-45 weight part, More preferably, it is 15-40 weight part, Especially preferably, it is 20-40 weight part, Most preferably, it is 20-35 weight part. The content of the low viscosity resin (B) described above is particularly preferably suitable when the high viscosity resin (A) is a hydrogenated or non-hydrogenated styrene elastomer, and the low viscosity resin (B) is a polyphenylene ether compound. .

Phosphorus Compound (C)

The phosphorus compound (C) contained in the resin composition of this invention functions as a flame retardant, and is a following formula (I):

(Wherein n is 3 to 4)

It is a cyclic cyanophenoxyphosphazene compound represented by. The phosphorus compound may be a mixture of n = 3 compound in the above formula and n = 4 compound in formula (I). For example, FP-300 by Fushimi Seiyakusho Co., Ltd. is mentioned as a product example of a compound of n = 3 in Formula (I), and the compound of n = 3 in Formula (I); As a product example of the mixture of the compound of n = 4, FP-300B by Fushimi Seiyakusho Co., Ltd. is mentioned.

It is preferable that content of the phosphorus compound (C) in the resin composition of this invention is 10-50 weight part, making the total amount of high viscosity resin (A), low viscosity resin (B), and phosphorus compound (C) 100 weight part. More preferably, it is 15-45 weight part, More preferably, it is 15-40 weight part, Especially preferably, it is 18-38 weight part, Most preferably, it is 20-35 weight part. The content of the phosphorus-based compound (C) described above is particularly preferably suited when the high-viscosity resin (A) is a hydrogenated or non-hydrogenated styrene-based elastomer, and the low-viscosity resin (B) is a polyphenylene ether compound.

Filler (D)

In this specification, a "filler" means what exists in a resin composition as a filler single phase, without making it compatible in a resin composition. The filler may or may not have a surface treatment layer on the filler surface, and the surface treatment layer may or may not be compatible with the resin component in the resin composition. The filler (D) contained in the resin composition of this invention is not specifically limited, Various fillers generally used for addition to a resin composition can be used. Therefore, the filler may be either an organic filler or an inorganic filler, but an inorganic filler is preferred from the viewpoint of electrical properties and flame retardancy. Examples of the inorganic fillers include silica, talc, boron nitride (BN), and the like. The inorganic filler is not particularly limited as long as it can be dispersed in the resin composition, but silica is preferable in view of dispersibility and dielectric properties. The organic filler is not particularly limited as long as it is incompatible with the high viscosity resin (A) and the low viscosity resin (B), but a fluorine-based organic filler is preferable from the viewpoint of dielectric properties and flame retardancy.

It is preferable that filler (D) is an inorganic filler. The average particle diameter D50 of the inorganic filler is preferably 0.1 to 3 mu m, more preferably 0.3 to 1.5 mu m. By using the silica particle (for example, spherical silica particle) which has an average particle diameter D50 in the said range, the resin composition excellent in fluidity | liquidity and workability can be provided. The filler (D) may be in any form such as pulverized particles, spherical particles, core shell particles, hollow particles and the like.

It is preferable that content of the filler (D) in the resin composition of this invention is 5-200 weight part, making the total amount of high viscosity resin (A), low viscosity resin (B), and a phosphorus compound (C) 100 weight part. More preferably, it is 25-190 weight part, More preferably, it is 45-180 weight part, Especially preferably, it is 90-170 weight part, Most preferably, it is 110-160 weight part. The content of the above-mentioned filler (D) is particularly preferably suited when the high viscosity resin (A) is a hydrogenated or non-hydrogenated styrene elastomer, and the low viscosity resin (B) is a polyphenylene ether compound.

Usage

Since the resin composition of this invention is excellent in various characteristics, such as a circuit buried property and handling property (flexibility), at the time of circuit formation, and shows low dielectric loss tangent and excellent flame retardance after hardening, insulation of the printed wiring board suitable for a high frequency use is carried out. Particularly suitable for layers. That is, it is preferable that the resin composition of this invention is used for the insulating layer for wiring boards. Therefore, according to the preferable aspect of this invention, the insulating layer for wiring boards which hardens a resin composition is provided. Moreover, according to another preferable aspect of this invention, the laminated body provided with the resin layer which hardens a resin composition on the surface of a metal layer is provided.

Example

This invention is demonstrated further more concretely by the following example.

Example 1-16

(1) preparation of raw materials

First, various raw materials shown in Table 1 were prepared. The detail of each raw material is as follows.

<High viscosity resin (A)>

MP-10 (Hydrogenated styrene-based elastomer, manufactured by Asahi Kasei Co., Ltd., viscosity at 120 ° C: 75400 Pa.s)

HG-252 (SEEPS-OH: polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene, terminal hydroxyl group modification, Kuraray Co., Ltd. viscosity at 120 ° C: 10060 Pa.s)

<Low viscosity resin (B)>

V-03 (carbodiimide resin, Nisshinbo Chemical Co., Ltd. make, viscosity at 120 degreeC: less than 8000 Pa.s)

OPE-2St-1200 (a styrene derivative of a bifunctional polyphenylene ether oligomer, manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight about 1200, viscosity at 120 ° C: less than 8000 Pa.s)

OPE-2St-2200 (a styrene derivative of a bifunctional polyphenylene ether oligomer, manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight about 2200, viscosity at 120 ° C: less than 8000 Pa · s)

SA-90 (bifunctional polyphenylene ether oligomer, product of SABIC, viscosity at 120 degreeC: less than 8000 Pa.s)

<Phosphorus Compound (C)>

FP-300B (cyclic cyanophenoxyphosphazene compound, Fushimi Seiyakusho Co., Ltd. compound of n = 3-4 in Formula (I))

FP-110 (cyclic phenoxy phosphazene compound, Fushimi Seiyakusho Co., Ltd., compound which does not satisfy Formula (I))

SPH-100 (cyclic hydroxyphenoxyphosphazene compound, manufactured by Otsuka Chemical Co., Ltd., a compound that does not satisfy formula (I))

<Filler (D)>

SC4050 (Average particle diameter D50: 1.0 micrometer measured by spherical silica particle, the Admatex make, laser diffraction type particle size distribution measurement)

(2) preparation of varnishes

In the raw material name and solid content weight ratio shown in Table 1, the high viscosity resin, the low viscosity resin (except Example 15), the phosphorus compound (except Example 14), and the filler (except Example 16), so that the solid content concentration is 50%. Toluene solvent was added and melt-dispersed using the disperser at 60 degreeC. In this way, the adjusted resin solution (varnish) was obtained.

(3) Preparation of Copper Foil with Resin in Semi-Hermed State (B-stage)

The obtained resin solution is dried using a comma coating machine on the surface of an electrolytic copper foil (TQ-M4-VSP foil, manufactured by Mitsui Kinzoku Kogyo Co., Ltd., 18 µm thick, 0.4 µm of 10-point average roughness (Rzjis)). It applied so that the thickness of the subsequent resin layer might be set to 130 micrometers. The resin composition was semi-hardened by drying a coating film at 150 degreeC for 3 minutes. In this way, the copper foil with resin which provided the resin layer of semi-hardened state (B-stage) was produced.

(4) Production of resin film alone

Copper foil with two resins was bonded together so that their resin layers could contact each other, and hot vacuum press molding was performed under heat and press conditions of 30 kgf / cm 2 for 90 minutes at 200 ° C. to manufacture a double-sided copper clad laminate. Both copper of both surfaces of the obtained copper clad laminated board was removed by etching, and the resin film as a single body was obtained.

(5) various evaluations

The following various evaluations were performed about the resin film obtained by said (4), or the copper foil provided with resin of the semi-hardened state obtained by said (3).

(5a) dielectric properties

For the resin film alone, the dielectric constant Dk and the dielectric tangent Df at 10 Hz were measured by the perturbation cavity resonant technique. This measurement was performed in accordance with JIS R 1641 using a measuring device (a resonator made by KEYCOM and a network analyzer made by KEYSIGHT) after cutting the resin film alone in accordance with the sample size of the resonator. The measured Df value was graded based on the following criteria.

<Dielectric property evaluation criteria>

Evaluation A: Df value at 10 Hz is less than 0.0020

-Evaluation B: Df value in 10 Hz is 0.0020 or more and less than 0.0025

-Evaluation C: Df value in 10 Hz is 0.0025 or more and less than 0.0030

-Evaluation D: Df value in 10 Hz is 0.0030 or more

(5b) glass transition temperature (Tg)

For the resin film alone, the peak temperature of Tanδ was measured as the glass transition temperature (Tg) by dynamic viscoelasticity measurement (DMA: Dynamic Mechanical Analysis). This measurement was performed using the dynamic viscoelasticity measuring apparatus (DMS6100 by Seiko Instruments Co., Ltd.) based on JISC6481. The measured glass transition temperature (Tg) was graded based on the following references | standards.

<Glass Transition Temperature (Tg) Evaluation Criteria>

Evaluation A: Tg is 170 degreeC or more

Evaluation B: Tg is 150 degreeC or more and less than 170 degreeC

Evaluation C: Tg is 130 degreeC or more and less than 150 degreeC

Evaluation D: Tg is less than 130 ° C

(5c) handling

The handling property evaluation of the resin film single piece was performed in the following procedures. First, the resin film single piece of size 10 cm x 30 cm and thickness 250 micrometers was prepared. The short side of this resin film single side was fixed to a horizontal clamp, and the other short side was lifted vertically to the high position of 15 cm from the clamp, and then the resin film single piece was removed. Visually confirm the presence or absence of cracking of the resin film when the resin film falls and bends due to its own weight, and visually confirms the presence or absence of whitening when the sample is bent at an angle of 180 °. Rated by.

<Handlingability evaluation criteria>

Evaluation A: The resin film did not crack and whitening did not occur.

-Evaluation B: Although the resin film did not crack, whitening generate | occur | produced.

Evaluation D: The resin film was cracked.

Here, "whitening" refers to a thing which appears to be clouded because a fine crack generate | occur | produces inside when a stress is added to a resin film.

(5d) resin flow

Four sheet pieces which are a size of 10 cm x 10 cm were cut out from the copper foil (resin layer thickness 130 micrometers) with resin of semi-hardened state (B-stage). These 4 sheet pieces were laminated | stacked so that the resin-copper foil layer might be crossed, and it was set as the sample. The obtained sample was subjected to a hot press treatment at a pressure of 14 kgf / cm 2 for 10 minutes at 170 ° C using a heat press. The resin flow was measured by dividing the weight of resin which protruded from the area of 10 cm x 10 cm which is an original size by the original resin weight, and multiplying the obtained value by 100. The resin flow value measured was graded based on the following criteria.

<Resin Flow Evaluation Criteria>

Evaluation A: The resin flow value is larger than 1.0% and 5.0% or less

Evaluation B: The resin flow value is greater than 0.0% and 1.0% or less, or greater than 5.0% and 10.0% or less

Evaluation C: The resin flow value is greater than 10.0% and less than 20.0%

Evaluation D: The resin flow value is greater than 0.0% or 20.0%

(5e) flame retardant

The resin film alone was subjected to a vertical combustion test in accordance with the UL94 standard, and evaluated according to the following criteria.

<Flame Retardation Evaluation Criteria>

Evaluation A: V-0 evaluation in UL94 standard

Evaluation B: V-1 evaluation in UL94 standard

Evaluation C: V-2 evaluation in UL94 standard

Evaluation D: HB evaluation in UL94 standard

(5f) circuit embedding

The copper foil (resin layer thickness 130 micrometers) with resin of semi-hardened state (B-stage) is laminated | stacked on the board | substrate which formed the circuit pattern (circuit height 35 micrometers), and a circuit pattern in the insulating layer which consists of resin layers This buried laminate was obtained. In the obtained laminate, it was checked whether (i) voids exist and (ii) the required insulation layer thickness (specifically, within 95 µm ± 10% from the top of the circuit) could be ensured. Rated by.

Buried Evaluation Criteria

Evaluation A: The required insulation layer thickness was secured, and no void was present.

Evaluation B: Voids do not exist but the necessary insulation layer thickness cannot be obtained, or an insulation layer thickness is secured but voids exist.

Evaluation D: The required insulation layer thickness was not secured and voids were present.

(5g) evaluation result

The evaluation results were as shown in Table 1 and Table 2.

Claims (15)

Cyanate compound, polyarylene ether compound, cycloolefin compound, hydrogenated or non-hydrogenated styrene-based elastomer, polyimide compound, siloxane compound, polyalkyl compound, and epoxy having a viscosity at 120 ° C. or higher. At least one high viscosity resin (A) selected from the group consisting of compounds having a reaction mechanism that does not generate hydroxyl groups when reacting with the compound,
Cyanate compound, polyarylene ether compound, cycloolefin compound, hydrogenated or non-hydrogenated styrene-based elastomer, polyimide compound, siloxane compound, polyalkyl compound, and epoxy having a viscosity at 120 ° C. of less than 8000 Pa · s At least one low viscosity resin (B) selected from the group consisting of compounds having a reaction mechanism that does not generate hydroxyl groups when reacting with the compound,
Formula (I):

(Wherein n is 3 or 4)
Phosphorus-based compound (C) represented by
Fillers (D) which are organic or inorganic fillers
Comprising a resin composition. The resin composition of Claim 1 whose said filler (D) is an inorganic filler. The resin composition of Claim 2 whose said inorganic filler is silica particle whose average particle diameter D50 is 0.1-3 micrometers. The said high viscosity resin (A) and / or the said low viscosity resin (B) contains a polyphenylene ether compound as said polyarylene ether compound, The said polyphenyl in any one of Claims 1-3. The ene ether compound has the following formula:

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, n is a repeating number)
The resin composition which is a compound containing the skeleton represented by in a molecule | numerator. The said high viscosity resin (A) and / or the said low viscosity resin (B) contains the said cyanate compound, The said cyanate compound is a cyanate group or a tree of any one of Claims 1-4. The resin composition which is an organic compound containing an azine skeleton. The said high viscosity resin (A) and / or said low viscosity resin (B) contains the said cycloolefin compound, The said cycloolefin compound is a following formula in any one of Claims 1-5,

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently —H or an alkyl group having 1 to 5 carbon atoms and n is 1 to 3000)
A compound containing a dicyclopentadiene skeleton represented by the formula, or the following formula:

(Wherein X is —CH ₂ — or —C ₂ H ₄ —, R ₁ , R ₂ , R ₃ and R ₄ are each independently —H or an alkyl group having 1 to 5 carbon atoms, n is 0 to 2 , m is from 1 to 1000)
A compound containing a norbornene skeleton represented by the formula, or the following formula:

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently —H or an alkyl group having 1 to 5 carbon atoms and n is 1 to 3000)
The resin composition which is a compound containing the indane skeleton represented by these. The resin composition according to any one of claims 1 to 6, wherein the high viscosity resin (A) and / or the low viscosity resin (B) contains the styrene-based elastomer. The resin composition according to any one of claims 1 to 7, wherein the high viscosity resin (A) and / or the low viscosity resin (B) contains the polyimide compound. The resin composition according to any one of claims 1 to 8, wherein the high viscosity resin (A) and / or the low viscosity resin (B) contains the siloxane compound. The polyphenylene ether according to any one of claims 1 to 4 and 7, wherein the high viscosity resin (A) is the styrene-based elastomer, and the low viscosity resin (B) is the polyarylene ether compound. A resin composition, which is a compound. The said high viscosity as described in any one of Claims 1-10 whose total viscosity of the said high viscosity resin (A), the said low viscosity resin (B), and the said phosphorus compound (C) is 100 weight part, and the said high viscosity A resin composition comprising a resin (A), 10 to 50 parts by weight of the low viscosity resin (B), 10 to 50 parts by weight of the phosphorus compound (C), and 5 to 200 parts by weight of the filler (D). 20 to 70 parts by weight of the high viscosity resin (A), 15 to 40 parts by weight of the low viscosity resin (B), 15 to 40 parts by weight of the phosphorus compound (C), and 45 to 180 weight The resin composition containing negative said filler (D). The insulating layer for wiring boards which hardens the resin composition in any one of Claims 1-12. The resin composition as described in any one of Claims 1-12 whose dielectric loss tangent in 10 GPa after hardening is less than 0.003. The laminated body provided with the resin layer formed by hardening | curing the resin composition in any one of Claims 1-12 and 14 on the surface of a metal layer.