WO2019021862A1

WO2019021862A1 - Resin composition, insulating layer for wiring board, and laminate

Info

Publication number: WO2019021862A1
Application number: PCT/JP2018/026513
Authority: WO
Inventors: 和弘大澤; 敏文松島; 孝宏本郷
Original assignee: 三井金属鉱業株式会社
Priority date: 2017-07-27
Filing date: 2018-07-13
Publication date: 2019-01-31
Also published as: MY195223A; CN110709476A; KR20190133787A; TW201910411A; JPWO2019021862A1; JP7219216B2; TWI739017B; KR102254544B1

Abstract

Provided is a resin composition which is excellent in terms of various properties including flame retardancy, circuit embedding property, and handleability (flexibility) and which nevertheless can bring about a significantly low dielectric dissipation factor. The resin composition comprises a given high-viscosity resin (A) having a viscosity at 120°C of 8,000 Pa∙s or higher, a given low-viscosity resin (B) having a viscosity at 120°C less than 8,000 Pa∙s, a phosphorus compound (C) represented by the formula (wherein n is 3 or 4), and a filler (D) which is an organic filler or inorganic filler.

Description

Resin composition, insulating layer for wiring board and laminate

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 the recent advancement of functions of portable electronic devices and the like, the frequency of signals has been increased, and a printed wiring board suitable for such high frequency applications has been required. A low transmission loss is desired for this high frequency printed wiring board in order to enable transmission without deteriorating the quality of high frequency signals. The printed wiring board is provided with a copper foil processed into a wiring pattern and an insulating resin base, but the transmission loss is mainly the conductor loss caused by the copper foil and the dielectric loss caused by the insulating resin base It consists of Therefore, in the copper foil with a resin layer applied to high frequency applications, it is desirable to suppress the dielectric loss caused by the resin layer. For this purpose, the resin layer is required to have excellent dielectric properties, particularly a low dielectric loss tangent.

The materials for printed wiring boards are also required to have properties such as flame retardancy, heat resistance, and peel strength with copper foil, etc. Various resin compositions have been proposed to satisfy such requirements. In particular, a resin having a low dielectric loss tangent tends to be inferior in flame retardancy in many cases, so that it is desirable to add a flame retardant to the resin composition. Although halogen compounds are known as such flame retardants, they are not preferable from the environment because of harmful substances such as dioxin generated at the time of incineration. In addition, compounds of halogen (for example, bromine etc.) except fluorine have poor dielectric properties.

Therefore, a resin composition containing a cyclophosphazene compound, which is a halogen-free flame retardant, has been proposed. For example, Patent Document 1 (WO 2015/133292) includes (A) polyphenylene ether (PPE) having a number average molecular weight of 500 to 5000, (B) a cyclophosphazene compound containing 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, flame retardancy, thermal expansion coefficient, and moisture absorption are disclosed. It is said that a printed wiring board with excellent heat resistance can be provided.

On the other hand, resin compositions containing cyanophenoxy-modified phosphazene are known as flame retardant resin compositions suitable as solder resists for flexible printed wiring boards. For example, Patent Document 2 (Japanese Patent Laid-Open No. 2009-191252) includes (A) carboxyl group- and ethylenic unsaturated group-containing urethane resin, (B) phenoxyphosphazene compound, (C) photopolymerization initiator, (D) Disclosed is a flame retardant resin composition comprising an ethylenically unsaturated group-containing compound, (E) a flame retardant component, (F) a thermosetting component, and (G) a thermosetting coagent. In this document, the phenoxy phosphazene compound is only positioned as a flame retardant excellent in compatibility with the urethane resin for solder resist, and no study on dielectric loss tangent is made.

International Publication No. 2015/133292 JP, 2009-191252, A

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 which the circuit was formed, and embedding a circuit with the resin layer as an insulating layer. However, since this work is carried out in a semi-cured state (B-stage), if the resin flowability (resin flow) is too high, it is not possible to ensure the necessary insulating layer thickness due to the outflow of the resin, but the resin If the fluidity (resin flow) of the resin is too low, the insulating layer will be cured while having an undesirable void (void). That is, if the resin flow is too high or too low, the circuit embedding property is reduced, so it is desirable to design the composition very carefully in consideration of the fluctuation of the characteristics. On the other hand, in the resin composition after curing (C-stage), it is desired to have various properties such as low dielectric loss tangent, excellent heat resistance, flame retardancy, handling property (flexibility) and the like. However, when attempting to design a composition that emphasizes the improvement of the circuit embedding property and the handling property (flexibility), various properties of the resin composition after curing are likely to be deteriorated, and in particular, the flame retardancy and dielectric properties (low dielectric loss tangent) It becomes difficult to achieve both. That is, while improving various properties (such as dielectric properties and flame retardancy) of the resin composition in the cured state (C-stage), the resin composition is also excellent in circuit embedding in the semi-cured state (B-stage). desired.

The inventors of the present invention have found that resin compositions containing a predetermined high viscosity resin (A), a predetermined low viscosity resin (B), a predetermined phosphorus compound (C), and a predetermined filler (D) are difficult to obtain. It has been found that, while being excellent in various properties such as flame retardancy, circuit embedding property, and handling property (flexibility), a significantly low dielectric loss tangent can be obtained.

Therefore, an object of the present invention is to provide a resin composition capable of providing significantly lower dielectric loss tangent while having excellent properties such as flame retardancy, circuit embedding property, and handling property (flexibility). is there.

According to one aspect of the invention:
Reacts with cyanate compounds, polyarylene ether compounds, cycloolefin compounds, hydrogenated or non-hydrogenated styrenic elastomers, polyimide compounds, siloxane compounds, polyalkyl compounds, and epoxy compounds, which have a viscosity of 8000 Pa · s or more at 120 ° C. At least one high viscosity resin (A) selected from the group consisting of compounds having a reaction mechanism which does not generate a hydroxyl group at the time of
React with cyanate compounds, polyarylene ether compounds, cycloolefin compounds, hydrogenated or non-hydrogenated styrenic elastomers, polyimide compounds, siloxane compounds, polyalkyl compounds, and epoxy compounds, which have a viscosity of less than 8000 Pa · s at 120 ° C. At least one low viscosity resin (B) selected from the group consisting of compounds having a reaction mechanism which does not generate a hydroxyl group at the time of
The following formula (I):

(Wherein n is 3 or 4)
And a phosphorus compound (C) represented by
A filler (D) which is an organic filler or an inorganic filler;
There is provided a resin composition comprising

According to another aspect of the present invention, there is provided a wiring board insulating layer obtained by curing the resin composition.

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

Resin Composition The resin composition of the present invention comprises a high viscosity resin (A), a low viscosity resin (B), a phosphorus compound (C), and a filler (D). The high viscosity resin (A) is a resin having a viscosity of 8000 Pa · s or more at 120 ° C., and cyanate compounds, polyarylene ether compounds, cycloolefin compounds, hydrogenated or non-hydrogenated styrenic elastomers, polyimide compounds, siloxane compounds And at least one member selected from the group consisting of polyalkyl compounds and compounds having a reaction mechanism which does not generate a hydroxyl group when reacting with an epoxy compound. The low viscosity resin (B) has a viscosity of less than 8000 Pa · s at 120 ° C., and cyanate compounds, polyarylene ether compounds, cycloolefin compounds, hydrogenated or non-hydrogenated styrenic elastomers, polyimide compounds, siloxane compounds, polyalkyls It is one or more selected from the group consisting of a compound and a compound having a reaction mechanism which does not generate a hydroxyl group when reacting with an epoxy compound. The phosphorus compound (C) is a cyclic cyanophenoxy phosphazene compound represented by the above-mentioned formula (I). The filler (D) is an organic filler or an inorganic filler. Thus, according to the resin composition containing the predetermined high viscosity resin (A), the predetermined low viscosity resin (B), the predetermined phosphorus compound (C), and the predetermined filler (D), the circuit embedding can be performed. While being excellent in various properties such as properties and handling properties (flexibility), it can provide significantly lower dielectric loss tangent and flame retardancy after curing. For example, the resin composition of the present invention preferably has a dielectric loss tangent at 10 GHz after curing of less than 0.0030, more preferably less than 0.0025, and still more preferably less than 0.0020. Although the lower limit value of the dielectric loss tangent is not particularly limited, it is typically 0.0001 or more.

High viscosity resin (A) and low viscosity resin (B)
The high-viscosity resin (A) contained in the resin composition of the present invention has a viscosity of at least 8000 Pa · s at 120 ° C., preferably 10000 to 300000 Pa · s, more preferably 50000 to 200 000 Pa · s, particularly preferably 70000 to It is 150000 Pa · s. On the other hand, the low viscosity resin (B) contained in the resin composition of the present invention has a viscosity at 120 ° C. of less than 8000 Pa · s, preferably 5000 Pa · s or less, more preferably 1000 Pa · s or less, particularly preferably 0 It is .0001 to 10 Pa · s. By mixing two types of resins in this manner, it is possible to realize a desirable resin flow to improve the circuit embedding property at the time of circuit formation, and to improve the handling property (flexibility).

The “viscosity at 120 ° C.” referred to in the present specification refers to a JIS-Rheometer (dynamic visco-elasticity measuring device) (HAAKE MARS manufactured by Thermo Scientific) with respect to a semi-cured state (B-stage). According to K7117, it shall measure by the following methods. That is, a resin sample of 10 mm in diameter × 100 μm in thickness is placed between a plate of 10 mm in diameter and a flat plate of a torque measurement portion of 10 mm in diameter, and the temperature is raised at an angular velocity of 6.2832 rad / s and a heating rate of 2 ° C./min. The viscosity at 120 ° C. was measured. The viscosity was measured three times and an average value of three times was 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 styrenic elastomer, a polyimide compound, a siloxane compound, a polyalkyl It is selected from the group consisting of a compound and a compound having a reaction mechanism which does not generate a hydroxyl group when reacting with an epoxy compound. These compounds either provide low dielectric properties (e.g., a dielectric loss tangent of less than 0.005 at 10 Gz) either as such (for polymers) or when cured with the addition of curing agents (for monomers). It is a thing.

According to a preferred embodiment of the present invention, the high viscosity resin (A) and / or the low viscosity resin (B) can comprise 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 can be any organic compound containing a cyanato group or a triazine skeleton, and is not particularly limited. The functional number of the compound containing a cyanate group may be monofunctional or polyfunctional and is not particularly limited, but from the viewpoint of crosslinking and curing, polyfunctional is preferable for resin-coated copper foil (RCC). Examples of compounds containing a cyanate group include phenol novolac cyanate, cresol novolac cyanate, dicyclopentadiene novolac cyanate, biphenyl novolac cyanate, bisphenol A dicyanate, bisphenol F dicyanate, dicyclopentadiene dicyanate, and biphenyl diphenol. Cyanate etc. are mentioned. These cyanate compounds may be used alone or in combination of two or more. On the other hand, in the case of a cyanate compound containing a triazine skeleton, there is no particular limitation as long as it is a compound containing a skeleton in which one or two or more compounds of a cyanate compound containing a cyanato group are trimerized. The triazine skeleton may or may not contain a reactive functional group, but it is preferable for the resin-coated copper foil (RCC) to be easy to use if it contains a reactive functional group from the viewpoint of crosslinking and curing.

According to a preferred embodiment of the present invention, the high viscosity resin (A) and / or the low viscosity resin (B) can comprise a polyarylene ether compound, preferably a polyphenylene ether compound. In particular, the low viscosity resin (B) more preferably contains a polyphenylene ether compound. In any case, the polyarylene ether compound or the polyphenylene ether compound has 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 is typically 4 to 1000) is there)
It is preferable that it is a compound which contains frame | skeleton represented by these in a molecule | numerator. Examples of polyphenylene ether compounds used for the low viscosity resin (B) include styrene derivatives of polyphenylene ether oligomers, terminal hydroxyl group-modified polyphenylene ether oligomers, terminal methacryl-modified polyphenylene ether oligomers, terminal glycidyl ether-modified polyphenylene ether oligomers and the like. Examples of products of styrene derivatives of polyphenylene ether oligomers include OPE-2St-1200 and OPE-2St-2200 manufactured by Mitsubishi Gas Chemical Co., Ltd. Examples of products of terminal hydroxyl group-modified polyphenylene ether oligomers include SA-90 and SA-120 manufactured by SABIC. As a product example of the terminal methacryl modified polyphenylene ether oligomer, SA-9000 manufactured by SABIC can be mentioned.

Particularly preferably, the polyphenylene ether compound used for the low viscosity resin (B) has the following formula:

(Wherein, n is 1 to 30, m is 1 to 30)
And a polyphenylene ether resin having a number average molecular weight of less than 3,000, and a more preferable number average molecular weight is 800 to 2800. Examples of products of polyphenylene ether resin satisfying the above formula include OPE-2St-1200 and OPE-2St-2200 manufactured by Mitsubishi Gas Chemical Co., Ltd. The number average molecular weight may be a value measured in terms of polystyrene by GPC (gel permeation chromatography) method.

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. The cycloolefin compound has 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)
A compound containing a dicyclopentadiene skeleton represented by the formula:

(Wherein, X is -CH ₂ - or _-C 2 _{H 4} - a and _an alkyl group of R _{1, R} 2, _{R 3} and _{R 4} are each independently -H or C 1-5, n is 0 to 2 and m is 1 to 1000)
Or a compound containing a norbornene skeleton represented by the 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 any of the compounds containing an indane skeleton represented by Examples of the cycloolefin compound include (i) dicyclopentadiene type epoxy resin, (ii) norbornene monomer, (iii) the above dicyclopentadiene skeleton, the above norbornene skeleton, and one or more skeletons selected from the above indane skeleton Cycloolefin polymers and the like can be mentioned. Examples of the cycloolefin-based polymer include ZEONOR (registered trademark) manufactured by ZEON Corporation, TOPAS (registered trademark) manufactured by Topas Advanced Polymers GmbH, and the like.

According to a preferred embodiment of the present invention, the high viscosity resin (A) and / or the low viscosity resin (B) may contain a styrenic elastomer. In particular, the high viscosity resin (A) more preferably contains a styrenic elastomer. In any case, the styrene-based elastomer may be either hydrogenated or non-hydrogenated. That is, the styrene-based elastomer is a compound containing a site derived from styrene and is a polymer which may contain a site derived from a compound having a polymerizable unsaturated group such as an olefin other than styrene. When a double bond is present at a site derived from a compound having a polymerizable unsaturated group of a styrenic elastomer, the double bond may be hydrogenated or may not be hydrogenated. It may be. Examples of styrene-based elastomers include TR manufactured by JSR Corporation, SIS manufactured by JSR Corporation, Tuftec (registered trademark) manufactured by Asahi Kasei Corporation, Septon (registered trademark) manufactured by Kuraray Co., Ltd., Hibler (registered trademark) manufactured by Kuraray Co., etc. Can be mentioned. In particular, it is preferable to use a hydrogenated styrene-butadiene elastomer as the 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) can contain a polyimide compound. The polyimide compound is a compound containing an imide skeleton, and the skeleton of the precursor acid anhydride 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 has the following formula:

(Wherein, R ₁ and R ₂ are each independently an alkyl group, a phenyl group or a siloxane skeleton branched to a side chain, and n is 1 to 100)
It is typical that it is a compound containing a siloxane skeleton represented by the above, but it is preferable to contain a skeleton or a functional group other than siloxane in terms of compatibility with other resins and reactivity. As an example of a siloxane compound, silicone oil etc. are mentioned. For example, from the viewpoint of reactivity and compatibility with other components, Shin-Etsu Chemical Co., Ltd. KF-8010, X-22-161A, X-22-2445 or Toray Dow Corning Co., Ltd. BY16-853U, BY16-855 Those obtained by optionally modifying or pre-polymerizing silicone oils having reactive functional groups such as these may be used.

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 has the following formula:

(Wherein, n is 2 to 100,000)
Although it is typical that it is a compound containing the alkyl skeleton represented by these, skeletons other than an alkyl skeleton can also be included arbitrarily. Examples of polyalkyl compounds, polyethylene, polypropylene, olefin copolymers such as manufactured by Mitsui Chemicals, Inc. APEL ^TM, include long-chain alkyl epoxy.

According to a preferred embodiment of the present invention, the high viscosity resin (A) and / or the low viscosity resin (B) can include a compound having a reaction mechanism which does not generate a hydroxyl group when reacting with the epoxy compound. In particular, the low viscosity resin (B) more preferably contains the above-mentioned compound. In any case, examples of the above compounds include imidazole, active esters, carbodiimides and the like, and carbodiimides are particularly preferable from the viewpoint of reactivity.

As described above, the high-viscosity resin (A) and the low-viscosity resin (B) can use the same or different resins except for viscosity, but as the high-viscosity resin (A), hydrogenated or non-hydrogenated styrenic elastomers It is particularly preferable to select the polyarylene ether compound as the low viscosity resin (B). And it is more preferable to select a polyphenylene ether compound as a polyarylene ether compound.

Although the content ratio of the various components of the resin composition of this invention can be optimized by the combination of each component and a content ratio is not specifically limited, content of high viscosity resin (A) is high viscosity The total amount of the resin (A), low viscosity resin (B) and phosphorus compound (C) is 100 parts by weight, preferably 10 to 80 parts by weight, more preferably 15 to 75 parts by weight, and still more preferably It is 20 to 70 parts by weight, particularly preferably 25 to 65 parts by weight, and most preferably 30 to 60 parts by weight. The content of the high viscosity resin (A) described above is particularly preferable when the high viscosity resin (A) is a hydrogenated or non-hydrogenated styrenic elastomer and the low viscosity resin (B) is a polyphenylene ether compound. apply.

On the other hand, the content of the low viscosity resin (B) in the resin composition of the present invention is 10 parts by weight based on the total amount of the high viscosity resin (A), the low viscosity resin (B) and the phosphorus compound (C). The amount is preferably about 50 parts by weight, more preferably 15 to 45 parts by weight, still more preferably 15 to 40 parts by weight, particularly preferably 20 to 40 parts by weight, and most preferably 20 to 35 parts by weight. The content of the low viscosity resin (B) described above is particularly preferable when the high viscosity resin (A) is a hydrogenated or non-hydrogenated styrenic elastomer and the low viscosity resin (B) is a polyphenylene ether compound. apply.

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

(Wherein n is 3 to 4)
It is a cyclic cyano phenoxy phosphazene compound represented by The phosphorus-based compound may be a mixture of the compound of n = 3 in the above formula and the compound of n = 4 in formula (I). For example, as an example of the product of n = 3 single compound in formula (I), FP-300 manufactured by Fushimi Pharmaceutical Co., Ltd. may be mentioned, and a mixture of n = 3 compound and n = 4 compound in formula (I) As an example of a product, FP-300B manufactured by Fushimi Pharmaceutical Co., Ltd. is mentioned.

The content of the phosphorus compound (C) in the resin composition of the present invention is 10 to 50 based on the total amount of the high viscosity resin (A), the low viscosity resin (B) and the phosphorus compound (C) as 100 parts by weight. It is preferable that it is part by weight, more preferably 15 to 45 parts by weight, still more preferably 15 to 40 parts by weight, particularly preferably 18 to 38 parts by weight, and most preferably 20 to 35 parts by weight. The content of the phosphorus compound (C) described above is particularly preferable when the high viscosity resin (A) is a hydrogenated or non-hydrogenated styrenic elastomer and the low viscosity resin (B) is a polyphenylene ether compound. apply.

Filler (D)
In the present specification, the term "filler" refers to one that does not compatibilize in the resin composition and is present in the resin composition as a filler single phase. The filler may or may not have a surface treatment layer on the surface of the filler, and the surface treatment layer may be or may be compatible with the resin component in the resin composition. You do not have to. The filler (D) contained in the resin composition of the present invention is not particularly limited, and various fillers generally used for addition to the 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 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 from the viewpoint 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 .

The filler (D) is preferably an inorganic filler. The average particle size D50 of the inorganic filler is preferably 0.1 to 3 μm, more preferably 0.3 to 1.5 μm. By using silica particles (for example, spherical silica particles) having an average particle diameter D50 within the above range, a resin composition having excellent flowability and processability can be provided. The filler (D) may be in any form such as crushed particles, spherical particles, core-shell particles, hollow particles and the like.

The content of the filler (D) in the resin composition of the present invention is 5 to 200 parts by weight based on 100 parts by weight of the total of high viscosity resin (A), low viscosity resin (B) and phosphorus compound (C). It is preferably part, more preferably 25 to 190 parts by weight, still more preferably 45 to 180 parts by weight, particularly preferably 90 to 170 parts by weight, and most preferably 110 to 160 parts by weight. The content of the above-described filler (D) is particularly preferably applied to the case where the high viscosity resin (A) is a hydrogenated or non-hydrogenated styrenic elastomer and the low viscosity resin (B) is a polyphenylene ether compound .

Applications The resin composition of the present invention is excellent in various properties such as circuit embedding property and handling property (flexibility) at the time of circuit formation, but exhibits low dielectric loss tangent and excellent flame retardancy after curing, so it is suitable for high frequency applications It is particularly suitable for the insulating layer of printed wiring boards of That is, it is preferable that the resin composition of this invention is used for the insulating layer for wiring boards. Therefore, according to a preferred embodiment of the present invention, there is provided a wiring board insulating layer obtained by curing a resin composition. Moreover, according to another preferable aspect of this invention, the laminated body provided with the resin layer formed by hardening a resin composition on the surface of a metal layer is provided.

The invention is further illustrated by the following examples.

Examples 1 to 16
(1) Preparation of Raw Materials First, various raw materials shown in Table 1 were prepared. Details of each raw material are as follows.

<High viscosity resin (A)>
MP-10 (hydrogenated styrenic elastomer, manufactured by Asahi Kasei Corporation, viscosity at 120 ° C .: 75400 Pa · s)
HG-252 (SEEPS-OH: polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene, modified terminal hydroxyl group, manufactured by Kuraray Co., Ltd., viscosity at 120 ° C .: 1,0060 Pa · s)
<Low viscosity resin (B)>
V-03 (carbodiimide resin, manufactured by Nisshinbo Chemical Co., Ltd., viscosity at 120 ° C .: less than 8000 Pa · s)
OPE-2St-1200 (Styrene derivative of difunctional 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 (Styrene derivative of difunctional 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 (Difunctional polyphenylene ether oligomer, manufactured by SABIC, Viscosity at 120 ° C .: less than 8000 Pa · s)
<Phosphorus Compound (C)>
FP-300B (cyclic cyanophenoxy phosphazene compound, manufactured by Fushimi Pharmaceutical Co., Ltd., a compound wherein n = 3 to 4 in the formula (I))
FP-110 (Cyclic phenoxy phosphazene compound, manufactured by Fushimi Pharmaceutical Co., Ltd., a compound not satisfying the formula (I))
SPH-100 (Cyclic hydroxy phenoxy phosphazene compound, manufactured by Otsuka Chemical Co., Ltd., a compound not satisfying the formula (I))
<Filler (D)>
SC 4050 (spherical silica particles, manufactured by Admatex Co., Ltd., average particle diameter D50 measured by laser diffraction particle size distribution measurement: 1.0 μm)

(2) Production of Varnish High viscosity resin, low viscosity resin (except Example 15), phosphorus compound (except Example 14) and filler (Example 16) of raw material name and solid weight ratio shown in Table 1 Toluene was added with a toluene solvent so that the solid concentration would be 50%, and dissolved and dispersed at 60 ° C. using a dispersing machine. The resin solution (varnish) thus prepared was obtained.

(3) Production of resin-coated copper foil in a semi-cured state (B-stage) The obtained resin solution was electrodeposited copper foil (TQ-M4-VSP foil, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 18 μm, ten-point average) It apply | coated so that the thickness of the resin layer after drying might be set to 130 micrometers using the comma coating machine on the surface of roughness (Rzjis) 0.4 micrometer. The resin composition was semi-cured by drying the coated film at 150 ° C. for 3 minutes. Thus, a resin-coated copper foil provided with a resin layer in a semi-cured state (B-stage) was produced.

(4) Production of resin film alone Two resin-coated copper foils are pasted together so that the resin layers are in contact with each other, and hot vacuum press is applied under heat and pressure conditions of 30 kgf / cm ² at 200 ° C. for 90 minutes. It was molded to produce a double-sided copper-clad laminate. All copper on both sides of the obtained copper clad laminate was removed by etching to obtain a resin film as a single body.

(5) Various evaluations The following various evaluations were performed about the resin-clad copper foil of the semi-hardened state obtained by said resin film single-piece | piece obtained by said (4) or said (3).

(5a) Dielectric Properties The dielectric constant Dk and the dielectric loss tangent Df at 10 GHz were measured for the resin film alone by the perturbation-type cavity resonator method. This measurement was performed according to 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 according to the sample size of the resonator. The measured Df values were rated based on the following criteria.
<Evaluation criteria for dielectric characteristics>
-Evaluation A: Df value less than 0.0020 at 10 GHz-Evaluation B: Df value at 10 GHz less than 0.0020-Evaluation C: Cf at 10 GHz less than 0.0025-Evaluation D : Df value at 10 GHz is 0.0030 or more

(5b) Glass transition temperature (Tg)
The peak temperature of Tan δ was measured as a glass transition temperature (Tg) by dynamic viscoelasticity measurement (DMA: Dynamic Mechanical Analysis) for the resin film alone. This measurement was performed using a dynamic viscoelasticity measuring device (DMS 6100 manufactured by Seiko Instruments Inc.) in accordance with JIS C 6481. The glass transition temperature (Tg) measured was rated based on the following criteria.
<Glass transition temperature (Tg) evaluation criteria>
-Evaluation A: Tg is 170 ° C or more-Evaluation B: Tg is 150 ° C or more and less than 170 ° C-Evaluation C: Tg is 130 ° C or more and less than 150 ° C-Evaluation D: Tg is less than 130 ° C

(5c) Handling property The handling property evaluation of the resin film single-piece was performed in the following procedures. First, a single resin film having a size of 10 cm × 30 cm and a thickness of 250 μm was prepared. One short side of this resin film alone was fixed to a horizontal clamp, and the other short side was vertically lifted from the clamp to a height of 15 cm, and then the resin film alone was released. The presence or absence of cracks in the resin film when the resin film fell and bent by its own weight was visually confirmed, and the presence or absence of whitening when the same sample was bent at an angle of 180 ° was visually confirmed and rated according to the following criteria .
<Handling evaluation criteria>
-Evaluation A: The resin film did not break and whitening did not occur.
-Evaluation B: The resin film did not break but whitening occurred.
-Evaluation D: The resin film was broken.
Here, "whitening" indicates that a stress is applied to the resin film to generate a fine crack inside and to appear white and cloudy.

(5d) Resin flow Four sheet pieces of a size of 10 cm × 10 cm were cut out from the resin-coated copper foil (resin layer thickness 130 μm) in a semi-cured state (B-stage). These four sheet pieces were laminated so that the resin-copper foil layer was alternately made into a sample. The obtained sample was heat-pressed at a pressure of 14 kgf / cm ² at 170 ° C. for 10 minutes using a heat press. The resin flow was measured by dividing the weight of the resin protruding from the original size area of 10 cm × 10 cm by the weight of the original resin and multiplying the obtained value by 100. The resin flow values measured were rated according to the following criteria.
<Resin flow evaluation criteria>
-Evaluation A: Resin flow value is more than 1.0% and not more than 5.0%-Evaluation B: Resin flow value is more than 0.0% and not more than 1.0%, or more than 5.0% and 10.0% Below-Evaluation C: Resin flow value is more than 10.0% and not more than 20.0%-Evaluation D: Resin flow value is more than 0.0% or 20.0%

(5e) Flame retardancy A vertical combustion test was performed on a resin film alone in accordance with the UL 94 standard, and the rating was evaluated on the basis of the following criteria.
<Flame retardancy evaluation criteria>
-Evaluation A: V-0 evaluation in UL 94 standard-Evaluation B: V-1 evaluation in UL 94 standard-Evaluation C: V-2 evaluation in UL 94 standard-Evaluation D: HB evaluation in UL 94 standard

(5f) Circuit embedding property A resin-deposited copper foil (resin layer thickness 130 μm) in a semi-cured state (B-stage) is laminated on a substrate on which a circuit pattern (circuit height 35 μm) is formed, and insulation made of resin layer A laminate having a circuit pattern embedded in the layer was obtained. In the resulting laminate, confirm (i) whether or not the void exists, and (ii) whether or not the required insulating layer thickness (specifically, within 95 μm ± 10% from the top of the circuit) can be secured. The rating was evaluated based on the following criteria.
<Embedability evaluation criteria>
-Evaluation A: The required insulating layer thickness can be secured, and no void exists.
-Evaluation B: There is no void, but the required insulating layer thickness can not be secured, or the insulating layer thickness can be secured but a void is present.
-Evaluation D: The required insulating layer thickness can not be secured, and voids are present.

(5 g) Evaluation results The evaluation results are as shown in Tables 1 and 2.

Claims

Reacts with cyanate compounds, polyarylene ether compounds, cycloolefin compounds, hydrogenated or non-hydrogenated styrenic elastomers, polyimide compounds, siloxane compounds, polyalkyl compounds, and epoxy compounds, which have a viscosity of 8000 Pa · s or more at 120 ° C. At least one high viscosity resin (A) selected from the group consisting of compounds having a reaction mechanism which does not generate a hydroxyl group at the time of
React with cyanate compounds, polyarylene ether compounds, cycloolefin compounds, hydrogenated or non-hydrogenated styrenic elastomers, polyimide compounds, siloxane compounds, polyalkyl compounds, and epoxy compounds, which have a viscosity of less than 8000 Pa · s at 120 ° C. At least one low viscosity resin (B) selected from the group consisting of compounds having a reaction mechanism which does not generate a hydroxyl group at the time of
The following formula (I):

(Wherein n is 3 or 4)
And a phosphorus compound (C) represented by
A filler (D) which is an organic filler or an inorganic filler;
A resin composition containing
The resin composition according to claim 1, wherein the filler (D) is an inorganic filler.
The resin composition according to claim 2, wherein the inorganic filler is silica particles having an average particle diameter D50 of 0.1 to 3 μm.
The high viscosity resin (A) and / or the low viscosity resin (B) contains a polyphenylene ether compound as the polyarylene ether compound, and the polyphenylene 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, and n is a repeating number)
The resin composition according to any one of claims 1 to 3, which is a compound containing in the molecule a skeleton represented by
The high viscosity resin (A) and / or the low viscosity resin (B) contains the cyanate compound, and the cyanate compound is an organic compound containing a cyanato group or a triazine skeleton. The resin composition as described in a term.
The high viscosity resin (A) and / or the low viscosity resin (B) contains the cycloolefin compound, and the cycloolefin compound has the following formula:

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

(Wherein, X is -CH 2 - or -C 2 H 4 - a and an alkyl group of R 1, R 2, R 3 and R 4 are each independently -H or C 1-5, n is 0 to 2 and m is 1 to 1000)
Or a compound containing a norbornene skeleton represented by the formula:

(Wherein, R 1 , R 2 , R 3 and R 4 are each independently —H or an alkyl group of 1 to 5 carbon atoms, and n is 1 to 3000)
The resin composition according to any one of claims 1 to 5, which is a compound containing an indane skeleton represented by
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 high viscosity resin (A) is the styrene-based elastomer, and the low viscosity resin (B) is a polyphenylene ether compound as the polyarylene ether compound, according to any one of claims 1 to 4 and 7. Resin composition.
10 to 80 parts by weight of the high viscosity resin (A), wherein the total amount of the high viscosity resin (A), the low viscosity resin (B) and the phosphorus compound (C) is 100 parts by weight; 11. Any one of claims 1 to 10, comprising: parts by weight of said low viscosity resin (B), 10 to 50 parts by weight of said phosphorus compound (C), and 5 to 200 parts by weight of said filler (D). The resin composition according to any one of the preceding claims.
20 to 70 parts by weight of the high viscosity resin (A), 15 to 40 parts by weight of the low viscosity resin (B), and 15 to 40 parts by weight of the phosphorus compound (C), 45 to 180 parts by weight The resin composition according to claim 11, comprising the filler (D) of
An insulating layer for wiring board, which is obtained by curing the resin composition according to any one of claims 1 to 12.
The resin composition according to any one of claims 1 to 12, wherein the dielectric loss tangent at 10 GHz after curing is less than 0.003.
A laminate comprising a resin layer obtained by curing the resin composition according to any one of claims 1 to 12 and 14 on the surface of a metal layer.