TW202342635A - Resin composition, prepreg, film with resin, metal foil with resin, metal-clad laminate, and printed wiring board - Google Patents

Abstract

A resin composition according to the present invention contains: a core-shell rubber (A) having a core that contains a silicone polymer and/or an acrylic polymer and a shell that contains a poly(methyl methacrylate), said rubber having a harness of 40 or less; a curable resin (B) that includes a maleimide compound (B1) and a benzoxazine compound (B2) having an allyl group; and an inorganic filler (C).

Description

Resin compositions, prepregs, resin-coated films, resin-coated metal foils, metal-clad laminates and printed wiring boards

The present disclosure generally relates to resin compositions, prepregs, resin-coated films, resin-coated metal foils, metal-clad laminates, and printed wiring boards. More specifically, it relates to a resin composition containing a curable resin, a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate, and a printed wiring board.

Japanese Patent Application Laid-Open No. 2016-074871 (hereinafter referred to as "Patent Document 1") discloses a copper-clad laminated board. This copper-clad laminate is manufactured using a bismaleimide resin composition. Furthermore, the bismaleimide resin composition contains a bismaleimine compound, a benzotrimethacrylate compound having an allyl group, and/or a naphthomethacrylate compound having an allyl group.

Patent Document 1 discloses that the bismaleimide resin composition may contain an inorganic filler.

However, as the content of the inorganic filler in the bismaleimide resin composition increases, the adhesion between the insulating layers in the copper-clad laminate may decrease. Therefore, while suppressing the decrease in adhesion, there is also a demand for low thermal expansion of copper-clad laminates. In addition, heat resistance and flame retardancy are further required.

The purpose of this disclosure is to provide a resin composition, a prepreg, a resin-attached film, a resin-attached metal foil, and a metal-clad material that can form a cured product that has low thermal expansion, adhesion, heat resistance, and flame retardancy. Laminated boards and printed wiring boards.

A resin composition according to one aspect of the present disclosure contains: core shell rubber (A), which has a core containing polysiloxane polymer and/or acrylic polymer and an outer shell containing polymethyl methacrylate, and The hardness is 40 or less; a curable resin (B), which contains a maleimide compound (B1) and an allyl-containing benzodiazepine compound (B2); and an inorganic filler (C).

A prepreg according to one aspect of the present disclosure includes: a base material; and a resin layer including the resin composition impregnated into the base material or a semi-hardened product of the resin composition.

A resin-attached film according to one aspect of the present disclosure includes: a resin layer including the aforementioned resin composition or a semi-hardened product of the aforementioned resin composition; and a support film that supports the aforementioned resin layer.

A resin-attached metal foil according to one aspect of the present disclosure includes a resin layer including the aforementioned resin composition or a semi-hardened product of the aforementioned resin composition; and a metal foil adhered to the aforementioned resin layer.

A metal-clad laminated board according to one aspect of the present disclosure includes: an insulating layer including a cured product of the aforementioned resin composition or a cured product of the aforementioned prepreg; and a metal layer that is adhered to the aforementioned insulating layer.

A printed wiring board according to one aspect of the present disclosure includes: an insulating layer including a cured product of the resin composition or a cured product of the prepreg; and conductor wiring formed on the insulating layer.

1. Summary The inventors of the present invention have been conducting research in order to obtain a resin composition that can form a cured product that has low thermal expansion, adhesion, heat resistance, and flame retardancy. First, in order to achieve a low thermal expansion coefficient, two methods were examined. The first method is to mix an inorganic filler into the resin composition. The second method involves blending an elastomer into the resin composition.

Any of the above methods can achieve a low thermal expansion coefficient. However, the problem with the first method is that as the content of the inorganic filler material increases, the adhesion of the cured product decreases. In addition, the problem of the second method is that the adhesion is reduced, and the heat resistance and flame retardancy may also be reduced.

However, we found that by adding a specific core shell rubber and a specific hardening resin, the above problems can be solved. That is, the inventors of the present invention have completed the following resin composition.

The resin composition of this embodiment contains core-shell rubber (A), curable resin (B), and inorganic filler (C). In particular, the core-shell rubber (A) has a core containing polysiloxane polymer and/or acrylic polymer and an outer shell containing polymethylmethacrylate. And the hardness of the core and shell rubber (A) is 40 or less. Moreover, the curable resin (B) contains a maleimide compound (B1) and an allyl group-containing benzodiazepine compound (B2).

According to this embodiment, since the resin composition contains all the above-mentioned components, a cured product having low thermal expansion, adhesion, heat resistance, and flame retardancy can be formed.

Here, adhesion mainly means the bonding strength between the insulating layers, but also means the bonding strength between the insulating layer and the metal layer (copper foil, etc.). Heat resistance can be evaluated by the glass transition temperature (Tg). The specific evaluation methods of each characteristic are as described in the examples. 2.Details (1) Resin composition (1.1)Composition

The resin composition of this embodiment contains core-shell rubber (A), curable resin (B), and inorganic filler (C). The resin composition preferably further contains a high molecular weight body (D). The resin composition preferably further contains a flame retardant (E). The resin composition may further contain other (F). Each ingredient is explained below. ＜Core shell rubber (A)＞

Core-shell rubber (A) is an aggregate of rubber particles, and each rubber particle has a core-shell type multi-layer structure. Rubber particles are formed from an inner core and an outer shell. At least one of the core and the outer shell is elastic. By including the core shell rubber (A) in the resin composition, the low thermal expansion property of the cured product of the resin composition can be improved.

The core can contribute to the strengthening and toughening of the hardened material of the resin composition. The core is granulated rubber. Rubber can be a copolymer or a homopolymer. Specifically, the core includes polysiloxane polymer and/or acrylic polymer.

The polysiloxane polymer is not particularly limited, and examples thereof include oligomers and polymers in which various silanes such as dimethylsilane are hydrolyzed and the silanol produced is dehydrated and condensed.

The acrylic polymer means any of a copolymer and a homopolymer containing acrylate and/or methacrylate as monomer units.

The inner core may also contain butadiene-based polymers, isoprene-based polymers, etc. The butadiene-based polymer means either a copolymer or a homopolymer containing butadiene as a monomer unit. Likewise, the isoprene-based polymer means any of a copolymer and a homopolymer containing isoprene as a monomer unit.

The shell is easily miscible with the hardening resin (B), which helps improve adhesion. The outer shell is present on the surface of the core. The shell system is composed of multiple graft chains. One end of each graft chain is bonded to the core surface to become a fixed end, and the other end is a free end. The graft chain can be a copolymer or a homopolymer. The outer shell contains polymethyl methacrylate. In addition, the outer shell may also include acrylic copolymer, polystyrene, etc. Acrylic copolymer means a copolymer containing acrylate and/or methacrylate as monomer units.

The hardness of the core shell rubber (A) is 40 or less, preferably 38 or less, and more preferably 37 or less. Here, hardness is a measured value using a type A durometer described in JIS K 6253 "Vulcanized rubber and thermoplastic rubber - Calculation method of hardness." If the hardness of the core shell rubber (A) is greater than 40, it may be impossible to achieve low thermal expansion of the hardened material of the resin composition. In addition, the lower limit value of the hardness of the core shell rubber (A) is not particularly limited, but is, for example, 30 or more.

The 50% volume average particle diameter (D50) of the core shell rubber (A) is preferably 0.01µm or more and 0.5µm or less, and more preferably 0.05µm or more and 0.3µm or less. Here, "50% volume average particle diameter" means the particle diameter (D50) of 50% of the cumulative value in the particle size distribution measured by a particle size distribution measuring device based on the laser scattering diffraction method. By having the 50% volume average particle size (D50) of the core shell rubber (A) be 0.01µm or more, the impact resistance of the hardened material can be further improved. When the 50% volume average particle size (D50) of the core-shell rubber (A) is 0.5µm or less, the core-shell rubber (A) can be easily and uniformly dispersed in the resin composition and, as a result, can be easily and uniformly dispersed in the hardened material. ＜Cure resin (B)＞

The curable resin (B) contains a maleimide compound (B1) and an allyl group-containing benzodiazepine compound (B2). Thereby, the heat resistance of the cured product of the resin composition can be improved.

The maleimide compound (B1) is a compound having at least one 5-membered ring (maleimide group) in which maleic acid is imidized. The maleimide compound (B1) is not particularly limited, and examples thereof include compounds represented by the following formula (b1-1), compounds represented by the following formula (b1-2), and compounds represented by the following formula (b1-3) (Biphenyl aralkyl maleimide resin), a compound represented by the following formula (b1-4) (diphenyl ether bismaleimide) and a compound represented by the following formula (b1-5) (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide) etc. [Chemical formula 1] [Chemical formula 2] [Chemical formula 3] [Chemical formula 4] [Chemical formula 5] The allyl group-containing benzoyl compound (B2) is a benzoyl compound having at least one allyl group. A benzoic acid compound is a compound having at least one benzoic acid ring.

The allyl group-containing benzoyl compound (B2) is not particularly limited, and examples thereof include benzoyl compounds having a structure represented by the following formula (b2-1) and compounds having a structure represented by the following formula (b2-2) benzodiazepine compounds with a structure and benzene compounds with a structure represented by the following formula (b2-3), etc. [Chemical formula 6] The mass ratio (B2/B1) of the allyl group-containing benzodiazepine compound (B2) to the maleimide compound (B1) is preferably 0.3 or more and 1.0 or less, more preferably 0.35 or more and 0.8 or less. When the mass ratio (B2/B1) is 0.3 or more, it is possible to suppress a decrease in adhesion to a metal layer (such as copper foil, etc.). When the mass ratio (B2/B1) is 1.0 or less, a decrease in the glass transition temperature (Tg) can be suppressed. ＜Inorganic filler(C)＞

Inorganic filler material (C) can effectively improve dimensional stability. That is, if the inorganic filler (C) is contained in the resin composition, the thermal expansion coefficient of the cured product of the resin composition can be easily reduced.

The inorganic filler (C) is not particularly limited, but preferably contains at least one compound selected from the group consisting of silica, talc, boehmite, magnesium hydroxide, aluminum hydroxide, and zinc molybdate. and tungsten compounds.

The 50% volume average particle diameter (D50) of the inorganic filler (C) is preferably 0.1µm or more and 2.0µm or less, more preferably 0.1µm or more and 0.8µm or less. ＜High molecular weight body (D)＞

The high molecular weight body (D) preferably contains at least one selected from the group consisting of an acrylic resin, a styrene-based copolymer, and a butadiene-based copolymer. Furthermore, the styrenic copolymer means a copolymer containing styrene as a monomer unit. Likewise, a butadiene-based copolymer means a copolymer containing butadiene as a monomer unit.

The acrylic resin preferably has a structure represented by the following formula (1), formula (2) and formula (3). [Chemical Formula 7] In the above formulas (1) to (3), x, y, and z represent mole fractions, and satisfy x+y+z≦1, 0<x≦0.2, 0.6≦y≦0.95, 0.05≦z≦0.2.

In the above formula (2), R1 is a hydrogen atom or a methyl group, and R2 includes at least one of a hydrogen atom, an alkyl group, an epoxypropyl group and an epoxidized alkyl group. .

In the above formula (3), R3 is a hydrogen atom or a methyl group, and R4 is Ph (phenyl), -COOCH ₂ Ph or -COO(CH ₂ ) ₂ Ph.

The main chain of the acrylic resin preferably has at least one structure represented by formula (1), at least one structure represented by formula (2), and at least one structure represented by formula (3).

When the main chain of the acrylic resin has the structures represented by formula (1), formula (2) and formula (3), the arrangement order of the structures represented by formula (1), formula (2) and formula (3) is not particularly limited. At this time, in the main chain of the acrylic resin, the structure represented by formula (1) may be continuous or discontinuous, the structure represented by formula (2) may be continuous or discontinuous, and the structure represented by formula (3) may be continuous or discontinuous. Continuously.

Here, it is supplementary to explain that R2 in the formula (2) contains at least one of a hydrogen atom, an alkyl group, an epoxypropyl group, and an epoxidized alkyl group. . On the premise, there is one R2 in the structure shown in formula (2). The description will be divided into a case where the acrylic resin has only one structure represented by formula (2) and a case where the acrylic resin has two or more structures represented by formula (2).

In the former case, that is, when the acrylic resin has a structure represented by formula (2), R2 is an epoxypropyl group or an epoxidized alkyl group.

In the latter case, that is, when the acrylic resin has more than two structures represented by formula (2), R2 in at least one structure represented by formula (2) is an epoxypropyl group or an epoxidized alkyl group, and the remaining R2 in the structure shown in formula (2) is a hydrogen atom or an alkyl group. Judging from the fact that R2 in at least one structure represented by formula (2) is an epoxypropyl group or an epoxidized alkyl group, R2 in all structures represented by formula (2) can also be an epoxypropyl group or an epoxidized alkyl group. Alkyl oxide.

The structure represented by formula (3) has Ph (phenyl), -COOCH ₂ Ph, and -COO(CH ₂ ) ₂ Ph. Ph, -COOCH ₂ Ph, -COO(CH ₂ ) ₂ Ph is thermally stable, so it can increase the strength of the cured resin composition, thereby improving the strength of the laminated board (metal-clad laminated board 4 and printed wiring board 5 ) heat resistance.

The high molecular weight body (D) is a substance having a weight average molecular weight (Mw) of 10,000 to 900,000, preferably 10,000 to 600,000. The high molecular weight body (D) can easily impart impact resistance and toughness to the cured product of the resin composition without impairing the heat resistance. ＜Flame retardant (E)＞

The flame retardant (E) is not particularly limited, and examples thereof include phosphorus-based flame retardants and halogen-based flame retardants. Among these, phosphorus-based flame retardants are preferred. If the resin composition contains a flame retardant (E), the flame retardancy of the cured product of the resin composition can be further improved.

The phosphorus-based flame retardant forms an oxygen barrier layer through the film of the phosphoric acid layer generated by thermal decomposition, and forms a carbon film on the resin surface through dehydration to block heat and heat, thereby imparting flame retardancy to the hardened material of the resin composition. sex. The phosphorus-based flame retardant is not particularly limited, and examples thereof include phosphine oxide compounds (stuylene bisdiphenylphosphine oxide) and phosphaphenanthrene-type phosphorus compounds. In particular, among the phosphaphenanthrene-type phosphorus compounds, a phosphaphenanthrene-type phosphorus compound having a reactive unsaturated group (for example, product name "SD-5" manufactured by SANKO Co., Ltd.) is preferred. ＜Others(F)＞

Others (F) are components that do not correspond to any of the core shell rubber (A), curable resin (B), inorganic filler (C), high molecular weight body (D), and flame retardant (E). Specific examples of other (F) are not particularly limited, and examples thereof include epoxy resin, hardener, hardening accelerator, catalyst (polymerization initiator), additives, and solvents.

Examples of epoxy resins include: bisphenol epoxy resin, novolac epoxy resin, biphenyl epoxy resin, stubble-based epoxy resin, arylalkylene-based epoxy resin, naphthalene-based epoxy resin, Triphenylmethane-type epoxy resin, anthracene-type epoxy resin, dicyclopentadiene-type epoxy resin, norvinyl-type epoxy resin, and nil-type epoxy resin, etc.

The hardener contains phenolic resin. The phenol resin is not particularly limited, and examples thereof include novolac-type phenol resin, cresol-novolak-type phenol resin, naphthalene-type phenol resin, biphenyl aralkyl-type phenol resin, dicyclopentadiene-type phenol resin, and the like.

The hardening accelerator contains imidazole compounds. The imidazole compound is not particularly limited, and examples thereof include 2-ethyl-4-methylimidazole and the like.

The catalyst contains organic peroxide. The organic peroxide is not particularly limited, and examples thereof include α,α'-di(tertiary butylperoxy)diisopropylbenzene (α,α'-Di(t-butylperoxy)diisopropylbenzene) and the like.

The additive is not particularly limited, and examples thereof include coupling agents, dispersing agents, and the like.

The solvent is not particularly limited, and examples thereof include methyl ethyl ketone (MEK) and the like. By adjusting the amount of solvent, the resin composition can be made into a varnish-like state. ＜Content relationship between ingredients＞

The content of the core shell rubber (A) is preferably not less than 1 part by mass and not more than 13 parts by mass, more preferably not less than 2 parts by mass and not more than 11 parts by mass, and more preferably not less than 3 parts by mass and not more than 100 parts by mass of the resin composition. 9 parts by mass or less.

The total content of the core shell rubber (A) and the curable resin (B) is preferably not less than 25 parts by mass and not more than 55 parts by mass, more preferably not less than 30 parts by mass and not more than 50 parts by mass, based on 100 parts by mass of the resin composition. More preferably, it is 35 parts by mass or more and 45 parts by mass or less.

The content of the core shell rubber (A) is preferably 3 parts by mass or more and 25 parts by mass or less, more preferably 5 parts by mass or more and less than 100 parts by mass of the total content of the core shell rubber (A) and the curable resin (B). 20 parts by mass or less.

The content of the inorganic filler (C) is preferably not less than 30 parts by mass and not more than 65 parts by mass, and more preferably not less than 40 parts by mass and not more than 60 parts by mass, based on 100 parts by mass of the resin composition.

When the resin composition further contains a high molecular weight body (D), the total content of the core shell rubber (A) and the high molecular weight body (D) is preferably 2 parts by mass or more and 15 parts by mass or less, based on 100 parts by mass of the resin composition. The content is preferably from 5 parts by mass to 13 parts by mass, and more preferably from 6 parts by mass to 12 parts by mass.

When the resin composition further contains a flame retardant (E), relative to the total of 100 of core shell rubber (A), curable resin (B), high molecular weight body (D), flame retardant (E) and others (F) Parts by mass, the content of the flame retardant (E) is preferably not less than 1 part by mass and not more than 20 parts by mass, more preferably not less than 5 parts by mass and not more than 15 parts by mass. (1.2) Manufacturing method

The resin composition of this embodiment can be produced by blending core-shell rubber (A), curable resin (B), and inorganic filler (C). High molecular weight (D) and/or flame retardant (E) may also be further blended as required. (2) Prepreg

The prepreg 1 of this embodiment is shown in FIG. 1 . The prepreg 1 can be used as a material of the printed wiring board 5, for example. The prepreg 1 includes a base material 11 and a resin layer 10 .

The base material 11 is formed with a plain texture, for example. That is, the base material 11 is formed by the vertical lines 111 and the horizontal lines 112 intersecting with each other. The base material 11 is not particularly limited, and examples thereof include glass cloth. The glass fiber contained in the glass cloth is not particularly limited, and examples thereof include E glass, S glass, Q glass, T glass, TS glass, NE glass, and L glass. Among these, from the viewpoint of low thermal expansion, S glass, Q glass, T glass, TS glass, NE glass and L glass are preferred. Therefore, the glass cloth should preferably contain at least one glass fiber selected from the group consisting of S glass, Q glass, T glass, TS glass, NE glass and L glass. In addition, the thickness of the base material 11 is not particularly limited.

The resin layer 10 includes a resin composition impregnated into the base material 11 or a semi-hardened product of the resin composition. The semi-cured resin composition is a resin composition in the intermediate stage (B stage) of the curing reaction. The thickness of the resin layer 10 is not particularly limited. (3) Film with resin

FIG. 2 shows the resin-attached film 2 of this embodiment. The resin-coated film 2 can be used, for example, as a build-up material. The resin-attached film 2 includes a resin layer 20 , a support film 21 and a protective film 22 .

The resin layer 20 contains a resin composition or a semi-hardened product of the resin composition. The thickness of the resin layer 20 is not particularly limited.

The support film 21 supports the resin layer 20 . The support film 21 is temporarily fixed on one side of the resin layer 20 . The support film 21 can be peeled off from the resin layer 20 as required.

The protective film 22 protects the resin layer 20 . And it is temporarily fixed on the other side of the resin layer 20 . The protective film 22 can be peeled off from the resin layer 20 if necessary. (4) Metal foil with resin

FIG. 3 shows the resin-attached metal foil 3 of this embodiment. The metal foil 3 with resin can be used as a build-up material, for example. The metal foil with resin 3 includes a resin layer 30 and a metal foil 31 .

The resin layer 30 contains a resin composition or a semi-hardened product of the resin composition. The thickness of the resin layer 30 is not particularly limited.

The metal foil 31 is adhered to one side of the resin layer 30 . The metal foil 31 is not particularly limited, and examples thereof include copper foil. (5)Metal clad laminate

The metal-clad laminate 4 of this embodiment is shown in FIG. 4 . The metal-clad laminated board 4 can be used as a material for the printed wiring board 5 . The metal-clad laminate 4 includes an insulating layer 40 and a metal layer 41 .

The insulating layer 40 includes a cured product of the resin composition or a cured product of the prepreg 1 . The insulating layer 40 is a layer having electrical insulation properties. The thickness of the insulating layer 40 is not particularly limited. A plurality of insulating layers 40 may be stacked and then connected. At this time, since the adhesion of the insulating layers 40 is high, it is difficult for the insulating layers 40 to be peeled off from each other.

The metal layer 41 is adhered to the insulating layer 40 . Since the insulating layer 40 has high adhesion, the metal layer 41 is not easily peeled off from the insulating layer 40 . In this embodiment, the metal layer 41 includes a first metal layer 411 and a second metal layer 412 . The first metal layer 411 is adhered to one side of the insulating layer 40 . The second metal layer 412 is adhered to the other side of the insulating layer 40 . That is, the metal-clad laminated board 4 shown in FIG. 4 is a double-sided metal-clad laminated board. The metal-clad laminate 4 may not have either the first metal layer 411 or the second metal layer 412 . At this time, the metal-clad laminated board 4 is a single-sided metal-clad laminated board. (6)Printed wiring board

The printed wiring board 5 of this embodiment is shown in FIG. 5 . Electronic components (not shown) are mounted on the printed wiring board 5 to form a printed circuit assembly. The printed wiring board 5 series is responsible for physically supporting the functions of electronic components. The printed wiring board 5 includes an insulating layer 50 and conductor wiring 51 .

The insulating layer 50 contains a cured product of the resin composition or a cured product of the prepreg 1 . The insulating layer 50 is a layer having electrical insulation properties. The thickness of the insulating layer 50 is not particularly limited. A plurality of insulating layers 50 may be laminated and then connected. At this time, since the adhesion of the insulating layers 50 is high, the insulating layers 50 are not easily peeled off from each other.

The conductor wiring 51 electrically connects electronic components to each other to form an electronic circuit. The conductor wiring 51 is formed on the insulating layer 50 . Since the insulating layer 50 has high adhesion, the conductor wiring 51 is not easily peeled off from the insulating layer 50 . In this embodiment, the printed wiring board 5 has two layers including conductor wiring 51 . That is, the conductor wiring 51 includes the first conductor wiring 511 and the second conductor wiring 512 . The first conductor wiring 511 is formed on one surface of the insulating layer 50 . The second conductor wiring 512 is formed on the other surface of the insulating layer 50 . The first conductor wiring 511 and the second conductor wiring 512 may be connected between layers.

The printed wiring board 5 may have three or more layers including the conductor wiring 51 . That is, the printed wiring board 5 may be a multilayer printed wiring board. 3. Appearance

As is apparent from the above embodiments, the present disclosure includes the following aspects. The following symbols are enclosed in parentheses only to express the corresponding relationship with the implementation form.

The first aspect is a resin composition containing: core shell rubber (A), which has a core containing polysiloxane polymer and/or acrylic polymer and an outer shell containing polymethylmethacrylate, and The hardness is 40 or less; a curable resin (B), which contains a maleimide compound (B1) and an allyl-containing benzodiazepine compound (B2); and an inorganic filler (C).

According to this aspect, it is possible to form a cured product that has low thermal expansion, adhesion, heat resistance, and flame retardancy.

A second aspect is a resin composition according to the first aspect. In the second aspect, the content of the core shell rubber (A) is 1 part by mass or more and 13 parts by mass or less based on 100 parts by mass of the resin composition.

According to this aspect, it is possible to form a cured product that has low thermal expansion, adhesion, heat resistance, and flame retardancy.

A third aspect is a resin composition according to the first or second aspect. In the third aspect, the mass ratio (B2/B1) of the allyl group-containing benzodiazepine compound (B2) to the maleimide compound (B1) is 0.3 or more and 1.0 or less.

According to this aspect, when the mass ratio (B2/B1) is 0.3 or more, it is possible to suppress a decrease in adhesion to a metal layer (for example, copper foil, etc.). When the mass ratio (B2/B1) is 1.0 or less, a decrease in the glass transition temperature (Tg) can be suppressed.

A fourth aspect is a resin composition according to any one of the first to third aspects. In the fourth aspect, it further contains a high molecular weight body (D), and the weight average molecular weight of the high molecular weight body (D) is 10,000 or more and 900,000 or less.

According to this aspect, impact resistance and toughness can be easily imparted to the hardened material of the resin composition without impairing the heat resistance.

A fifth aspect is a resin composition according to the fourth aspect. In the fifth aspect, the high molecular weight body (D) contains at least one selected from the group consisting of an acrylic resin, a styrene-based copolymer, and a butadiene-based copolymer.

According to this aspect, it is possible to form a cured product that has low thermal expansion, adhesion, heat resistance, and flame retardancy.

A sixth aspect is a resin composition according to the fourth or fifth aspect. In the sixth aspect, the total content of the core shell rubber (A) and the high molecular weight body (D) is 2 parts by mass or more and 15 parts by mass or less based on 100 parts by mass of the resin composition.

According to this aspect, it is possible to form a cured product that has low thermal expansion, adhesion, heat resistance, and flame retardancy.

A seventh aspect is a resin composition according to any one of the first to sixth aspects. In the seventh aspect, the inorganic filler (C) contains at least one compound selected from the group consisting of: silica, talc, boehmite, magnesium hydroxide, aluminum hydroxide, and molybdenum. Zinc acid and tungsten compounds.

According to this aspect, the thermal expansion coefficient of the cured product of the resin composition can be easily reduced.

An eighth aspect is a resin composition according to any one of the first to seventh aspects. In the eighth aspect, the content of the inorganic filler (C) is 30 parts by mass or more and 65 parts by mass or less based on 100 parts by mass of the resin composition.

According to this aspect, the thermal expansion coefficient of the cured product of the resin composition can be easily reduced.

A ninth aspect is a resin composition according to any one of the first to eighth aspects. In the ninth aspect, it further contains a flame retardant (E).

According to this aspect, the flame retardancy of the cured product of the resin composition can be further improved.

A tenth aspect is a prepreg (1), which is provided with: a base material (11); and a resin layer, which includes a resin layer impregnated into the base material (11) according to any one of the first to ninth aspects. The resin composition or the semi-hardened product of the aforementioned resin composition.

According to this aspect, it is possible to form a cured product that has low thermal expansion, adhesion, heat resistance, and flame retardancy.

An 11th aspect is a resin-attached film (2), which is provided with: a resin layer (20), which contains the resin composition according to any one of the 1st to 9th aspects or a semi-hardened product of the aforementioned resin composition. ; And a support film (21), which supports the aforementioned resin layer (20).

According to this aspect, it is possible to form a cured product that has low thermal expansion, adhesion, heat resistance, and flame retardancy.

A twelfth aspect is a metal foil (3) with resin, provided with: a resin layer (30), which contains a resin composition according to any one of the first to ninth aspects or a semi-hardened resin composition. and metal foil (31), which is adhered to the aforementioned resin layer (30).

According to this aspect, it is possible to form a cured product that has low thermal expansion, adhesion, heat resistance, and flame retardancy.

A 13th aspect is a metal-clad laminated board (4), provided with: an insulating layer (40), which contains a hardened product of the resin composition according to any one of the 1st to 9th aspects or according to the 9th aspect The cured product of the prepreg (1); and the metal layer (41), which is connected to the aforementioned insulating layer (40).

According to this aspect, it is possible to form a cured product that has low thermal expansion, adhesion, heat resistance, and flame retardancy.

A 14th aspect is a printed wiring board (5) provided with an insulating layer (50) containing a cured product of the resin composition according to any one of the 1st to 9th aspects or a resin composition according to the 9th aspect. A cured product of the prepreg (1); and a conductor wiring (51) formed on the insulating layer (50).

According to this aspect, it is possible to form a cured product that has low thermal expansion, adhesion, heat resistance, and flame retardancy.

Example Hereinafter, the present disclosure will be specifically explained through examples. However, the present disclosure is not limited by the following examples. 1. Sample (1) Resin composition (1.1)Raw materials ＜Core shell rubber (A)＞ ・Made by Mitsubishi Chemical Co., product name "S-2200", polysilicone/acrylic composite rubber, hardness: 37, D50: 0.1µm ・Made by Mitsubishi Chemical Co., product name "SX-005", polysilicone/acrylic composite rubber, hardness: 50, D50: 0.1µm ・Made by Mitsubishi Chemical Co., product name "SRK200A", polysilicone/acrylic composite rubber, hardness: 89, D50: 0.1µm ＜Cure resin (B)＞ ≪Maleimine compound (B1)≫ ・Manufactured by K･I Chemical Industry Co., LTD., product name "BMI-SE55", 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismale A mixture of acyl imine (compound represented by formula (b1-5)) and diphenyl ether bismaleimide (compound represented by formula (b1-4)) (mass ratio 1:1) ・Manufactured by Nippon Kayaku Co., Ltd., product name "MIR-3000", biphenyl aralkyl maleimide resin (compound represented by formula (b1-3)) ≪Allyl-containing benzophenone compounds (B2)≫ ・Made by Shikoku Chemical Industry Co., Ltd., product name "ALP-D" ≪Allyl-free benzoic acid compound (B3)≫ ・Made by Shikoku Chemical Industry Co., Ltd., product name "Pd". ＜Inorganic filler(C)＞ ・Made by Admatechs Co., Ltd., product name "SC2050-MTX", silicon dioxide, D50: 0.5µm ・Made by Admatechs Co., Ltd., product name "Z4SX-A1", zinc molybdate, spherical, D50: 0.8µm. ＜High molecular weight body (D)＞ ・Made by Nagase ChemteX Co., product name "PASR001", acrylic resin, weight average molecular weight: 500,000. ＜Flame retardant (E)＞ ・Manufactured by Jinyi Chemical Co., Ltd., product name "PQ60", phosphine oxide compound, styrylbisdiphenylphosphine oxide, phosphorus concentration 12.0%. ＜Others(F)＞ ・Made by DIC Co., Ltd., product name "TD-2090-60M", novolak type phenol resin, hydroxyl equivalent: 105g/eq ・Made by NOF Co., Ltd., product name "PERBUTYL P" α,α'-Di(t-butylperoxy)diisopropylbenzene (α,α'-Di(t-butylperoxy)diisopropylbenzene). (1.2) Manufacturing The resin composition was produced by blending each component at the blending ratio (parts by mass) shown in Table 1. (2) Prepreg The above-mentioned resin composition is impregnated into glass cloth (manufactured by Nitto Boji Co., Ltd., type #2118, WTX2116T, T glass, thickness 0.1mm), and then heated and dried at 130 to 150°C for about 2 to 5 minutes to produce Prepregs. (3)Metal clad laminate After laminating 8 pieces of the above-mentioned prepreg and further laminating copper foil (thickness 12µm) on both sides, heat and pressurize at 220°C, 2 hours, and 3MPa. In this way, a metal-clad laminated board (a copper-clad laminated board with a thickness of 0.8 mm) with copper foil bonded on both sides was produced. 2.Evaluation (1)Coefficient of thermal expansion (CTE) The copper foil of the metal-clad laminate was removed by etching to prepare an unclad plate, and a disk-shaped sample was cut out from the unclad plate. After drying the sample, a compressive load was applied using the TMA method, and the thermal expansion coefficient (CTE) of the sample in the in-plane direction below the glass transition temperature (Tg) was measured. The measured temperature is 50℃~260℃, and the temperature rising rate is 10℃/minute. In addition, if the coefficient of thermal expansion (CTE) is less than 7 ppm/°C, it is within the allowable range. The smaller the better. (2) Interlayer peel strength The outermost insulating layer (prepreg) was peeled off together with the copper foil from the metal-clad laminate, and the interlayer peel strength at this time was measured in accordance with JIS C 6481. Specifically, the insulating layer (prepreg) located on the outermost layer of the metal-clad laminate was peeled off together with the copper foil using a tensile testing machine at a speed of 50 mm/min, and the interlayer peeling strength at this time was measured. (kN/m). In addition, if the interlayer peeling strength is 0.20kN/m or more, it is within the allowable range, and the larger the better. (3)Heat resistance First, the copper foil on both sides of the metal-clad laminate is removed by etching to obtain an unclad board. Next, the glass transition temperature (Tg) of the uncoated plate was measured using a viscoelastic spectrometer "DMS100" manufactured by SEIKO INSTRUMENTS INC. At this time, dynamic viscoelasticity (DMA) was measured using the bending modulus and the frequency was set to 10 Hz, and the maximum loss tangent (tanδ) was displayed when the temperature was raised from room temperature to 320°C at a heating rate of 5°C/min. The temperature of the value is used as the glass transition temperature (Tg). Heat resistance was evaluated by glass transition temperature (Tg). In addition, if the glass transition temperature (Tg) is 270°C or above, it is within the allowable range, and the higher the better. (4)Flame retardancy Cut a test piece with a length of 125mm and a width of 12.5mm from the above metal-clad laminate. Then, the test piece was subjected to a burning test (vertical burning test) 10 times in accordance with Underwriters Laboratories' "Test for Flammability of Plastic Materials-UL94" (Plastic Materials Burning Test UL94). Specifically, two combustion tests were conducted on each of the five test pieces. The average burning duration during the burning test was calculated to evaluate the flame retardancy. In addition, if the average time is 5.0 seconds or less, it is within the allowable range, and the shorter the better.

[Table 1]

In Examples 1 to 7, it was confirmed that an insulating layer having all of low thermal expansion, adhesion, heat resistance, and flame retardancy can be formed.

In contrast, in Comparative Examples 1 to 4, it was confirmed that low thermal expansion properties could not be achieved.

1: Prepreg 10:Resin layer 11:Substrate 111: vertical line 112:Horizontal line 2: Film with resin 20:Resin layer 21: Support film 22:Protective film 3: Metal foil with resin 30:Resin layer 31:Metal foil 4:Metal clad laminate 40:Insulation layer 41:Metal layer 411: 1st metal layer 412: 2nd metal layer 5:Printed wiring board 50:Insulation layer 51: Conductor wiring 511: 1st conductor wiring 512: 2nd conductor wiring

FIG. 1 is a schematic cross-sectional view showing a prepreg according to an embodiment of the present disclosure.

FIG. 2 is a schematic cross-sectional view showing a resin-attached film according to an embodiment of the present disclosure.

FIG. 3 is a schematic cross-sectional view showing a metal foil with resin according to an embodiment of the present disclosure.

FIG. 4 is a schematic cross-sectional view of a metal-clad laminate according to an embodiment of the present disclosure.

FIG. 5 is a schematic cross-sectional view of a printed wiring board according to an embodiment of the present disclosure.

1: Prepreg

10:Resin layer

11:Substrate

111: vertical line

112:Horizontal line

Claims (14)

A resin composition containing: Core shell rubber (A), which has a core containing polysiloxane polymer and/or acrylic polymer and a shell containing polymethyl methacrylate, and has a hardness of less than 40; Hardening resin (B), which contains a maleimide compound (B1) and an allyl-containing benzodiazepine compound (B2); and Inorganic filler material (C). The resin composition of claim 1, wherein the content of the core shell rubber (A) is 1 to 13 parts by mass relative to 100 parts by mass of the resin composition. The resin composition according to claim 1, wherein the mass ratio (B2/B1) of the allyl-containing benzodiazepine compound (B2) to the maleimide compound (B1) is 0.3 or more and 1.0 or less. . The resin composition of claim 1 further contains a high molecular weight body (D), and the weight average molecular weight of the high molecular weight body (D) is 10,000 or more and 900,000 or less. The resin composition according to claim 4, wherein the high molecular weight body (D) contains at least one selected from the group consisting of acrylic resin, styrenic copolymer and butadiene copolymer. The resin composition of claim 4, wherein the total content of the core shell rubber (A) and the high molecular weight body (D) is 2 parts by mass or more and 15 parts by mass or less based on 100 parts by mass of the resin composition. The resin composition of claim 1, wherein the inorganic filler (C) contains at least one compound selected from the group consisting of: silica, talc, boehmite, magnesium hydroxide, hydrogen Aluminum oxide, zinc molybdate and tungsten compounds. The resin composition of claim 1, wherein the content of the inorganic filler (C) is 30 parts by mass or more and 65 parts by mass or less based on 100 parts by mass of the resin composition. The resin composition of claim 1 further contains a flame retardant (E). A prepreg is provided with: a base material; and a resin layer containing the resin composition according to any one of claims 1 to 9 or a semi-hardened product of the aforementioned resin composition impregnated into the base material. A resin-attached film is provided with: a resin layer including the resin composition according to any one of claims 1 to 9 or a semi-hardened product of the aforementioned resin composition; and a support film that supports the aforementioned resin layer. A metal foil with resin, comprising: a resin layer including the resin composition according to any one of claims 1 to 9 or a semi-hardened product of the resin composition; and a metal foil adhered to the resin layer. A metal-clad laminated board is provided with: an insulating layer including a hardened product of the resin composition according to any one of claims 1 to 9; and a metal layer connected to the insulating layer. A printed wiring board provided with: an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 9; and conductor wiring formed on the insulating layer.

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