CN108603003A

CN108603003A - Resin combination, prepreg, clad with metal foil plywood, resin sheet, printed circuit board and semiconductor device

Info

Publication number: CN108603003A
Application number: CN201780009567.7A
Authority: CN
Inventors: 铃木卓也; 浦滨成弘; 若林润
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2016-02-02
Filing date: 2017-01-27
Publication date: 2018-09-28
Anticipated expiration: 2037-01-27
Also published as: JPWO2017135168A1; JP6880510B2; TW201739820A; KR20180104290A; TWI781918B; CN108603003B; WO2017135168A1

Abstract

There is provided dielectric constant, dielectric loss angle tangent, it is fine wiring embeddability, heat resistance, excellent, with protective film and interlayer insulating film suitable for printed circuit board the physical property of developability resin combination, use its prepreg, clad with metal foil plywood, resin sheet, printed circuit board and semiconductor device.A kind of resin combination adheres to the fluorinated resin particle (A) and resin component (B) of silica dioxide granule containing surface.

Description

Resin combination, prepreg, clad with metal foil plywood, resin sheet, printed circuit board and Semiconductor device

Technical field

The present invention relates to resin combination, use its prepreg, clad with metal foil plywood, resin sheet, printed circuit board And semiconductor device.

Background technology

In recent years, in electronic equipment, communicator, personal computer etc. widely used semiconductor it is highly integrated fine Change and gradually accelerate, the data used in information communication communicate also in high speed and high capacity.Transmission in order to shorten signal is prolonged Late, transmission loss is reduced, low-k (low Dk) and low-dielectric loss angle tangent (low Df) are required to printed circuit board.For Realization these requirements are being carried out using having excellent electrical characteristics (low-k low-dielectric loss angle tangent) resin The research of composition.

In addition, due to the miniaturization of printed circuit board, densification, the lamination layer used in multilayer board is more Stratification, and require the miniaturization and densification of wiring.Therefore, for the resin combination used in the lamination layer, in order to embedding Thin wires in a subtle way, it is desirable that in forming with high heat resistance with high mobility and after the fine wiring of insertion.In this way Resin combination in, in order to keep electrical characteristics good, research apply fluororesin filler.For example, Patent Document 1 discloses passing through It is used together poly (phenylene ether) resin with fluororesin filler, to the excellent resin combination of electrical characteristics.In addition, patent document 2 In disclose by with fluororesin filler be used together norbornene resin to solidfied material electrical characteristics and excellent adhesion, Connect up the good resin combination of embeddability.

Existing technical literature

Patent document

Patent document 1：Japanese Unexamined Patent Application Publication 2006-516297 bulletins

Patent document 2：Japanese Unexamined Patent Publication 2007-177073 bulletins

Invention content

Problems to be solved by the invention

But the inventors of the present invention have found, there are various problems in the previous solidfied material for having used fluororesin filler.

For example, in patent document 1, the heat resistance of gained solidfied material is insufficient.

In addition, in patent document 2, the moisture absorption heat resistance after wiring is embedded is insufficient.

Therefore, the present invention makes in view of the above problems, provides dielectric when being used in multilayer board The excellent resin combination of constant, dielectric loss angle tangent, fine wiring embeddability, heat resistance, developability, the preimpregnation using it Material, clad with metal foil plywood, resin sheet, printed circuit board and semiconductor device.

The solution to the problem

The inventors of the present invention have found, by using the tree containing silica covering fluorinated resin particle (A) and resin component (B) Oil/fat composition can solve the above problems, so as to complete the present invention.

That is, the present invention includes content below.

(1) a kind of resin combination contains silica covering fluorinated resin particle (A) and resin component (B).

(2) according to the resin combination described in (1), wherein aforementioned silicas covers primary of fluorinated resin particle (A) The volume average particle size of grain is 5 μm or less.

(3) according to the resin combination described in (1) or (2), wherein aforementioned silicas covering fluorinated resin particle (A) exists Content in resin combination is 3~400 mass parts relative to 100 mass parts of resin solid content in resin combination.

(4) resin combination according to any one of (1)~(3), wherein aforementioned resin ingredient (B), which contains, to be selected from By maleimide compound, cyanate esters, epoxy resin, phenolic resin, oxetane resin, benzoxazine chemical combination It is more than any one of the group of object and compound composition with ethylenically unsaturated group.

(5) resin combination according to any one of (1)~(4), wherein also contain except aforementioned silicas covers Packing material (C) other than fluorinated resin particle (A).

(6) resin combination according to any one of (1)~(5), wherein also contain fire retardant (D).

(7) resin combination according to any one of (1)~(6), wherein also contain trigger for optical solidification (E).

〔8〕

According to the resin combination described in (4), wherein the aforementioned compound with ethylenically unsaturated group include selected from by At least one of group of the oligomer composition of 2 functionality phenylene ether oligomers and α-methylstyrene with vinyl with On.

〔9〕

According to the resin combination described in (4), wherein the aforementioned compound with ethylenically unsaturated group include selected from by Sour modified bisphenol F type rings oxygen (methyl) acrylate, the following general formula (1) compound represented and dipentaerythritol six (methyl) third It is more than at least one of group of olefin(e) acid ester composition.

(in formula (1), multiple R₁Each independently represent hydrogen atom or methyl, multiple R₂Each independently represent hydrogen atom or Methyl, multiple R₃Each independently represent substituent group or hydroxyl shown in substituent group, following formula (3) shown in following formula (2).).

(in formula (3), R₄Indicate hydrogen atom or methyl.).

〔10〕

According to the resin combination described in (9), wherein before the aforementioned compound with ethylenically unsaturated group includes at least State general formula (1) compound represented.

(11) a kind of prepreg, with base material and infiltration or described in any one of (1)~(10) that are coated on the base material Resin combination.

(12) a kind of clad with metal foil plywood has the prepreg described in stacking at least 1 or more (11) and configuration In the metal foil of the one or two sides of the prepreg.

(13) a kind of resin sheet, any one of (1)~(10) with supporter and the surface for being configured at the supporter The resin combination.

(14) a kind of printed circuit board, with the resin combination described in any one of (1)~(10).

(15) a kind of semiconductor device, with the resin combination described in any one of (1)~(10).

The effect of invention

In accordance with the invention it is possible to provide dielectric constant, dielectric loss angle tangent, fine wiring embeddability, heat resistance, development The resin combination of property physical property excellent, with protective film and interlayer insulating film suitable for printed circuit board uses its preimpregnation Material, clad with metal foil plywood, resin sheet, printed circuit board and semiconductor device.

Specific implementation mode

Hereinafter, to mode for carrying out the present invention (hereinafter referred to as " present embodiment ".) be described in detail.With Under present embodiment be for illustrate the present invention illustration, be not intended to limit the invention to content below.The present invention Suitable deformation can be carried out within the scope of its subject matter to implement.

It should be noted that " (methyl) acryloyl group " in this specification refers to " acryloyl group " and corresponding Both " methylacryloyl ", " (methyl) acrylate " refers to " acrylate " and corresponding " methacrylate " The two, " (methyl) acrylic acid " refer to both " acrylic acid " and corresponding " methacrylic acid ".In addition, this embodiment party In formula, for " resin solid content " or " resin solid content in resin combination ", unless otherwise specified, refer to then The ingredient in addition to solvent and packing material in resin combination, " 100 mass parts of resin solid content " refer to resin combination The ingredient in addition to solvent and packing material in object adds up to 100 mass parts.

The resin combination of present embodiment is characterized in that, contains silica covering fluorinated resin particle (A) and resin Ingredient (B).Hereinafter, being illustrated to each ingredient.

The silica covering fluorinated resin particle (A) used in present embodiment is the fluorine tree that surface is attached with silica Fat particle, with fluorinated resin particle and the silica dioxide granule for being attached to the fluororesin surface.As keeping silica dioxide granule attached It in the method on the surface of fluorinated resin particle, is not particularly limited, can be vibrated by merely mixing or applying upon mixing To implement.Attachment of the silica dioxide granule to fluorinated resin particle surface can carry out in the dry state.To fluorinated resin particle with The mixed proportion of silica dioxide granule is not particularly limited.Think even if for fraction of amount, as long as silica dioxide granule is present in The surface of fluorinated resin particle, it will be able to show flow behavior improvement caused by silica dioxide granule, this reality can be made The moisture absorption heat resistance applied the wiring embeddability of the resin combination of mode and connected up after insertion is good.

As the fluorinated resin particle used in the silica covering fluorinated resin particle (A) in present embodiment, without spy It does not limit, polytetrafluoroethylene (PTFE) (PTFE), tetrafluoroethylene-perfluoroalkyl ethylene oxy copolymer (PFA), tetrafluoride second can be enumerated The lithium propylene copolymer of alkene-(FEP), ethylene-chlorotrifluoro-ethylene copolymer (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), Kynoar (PVDF) etc..Wherein, from the viewpoint of electrical characteristics are excellent, preferably PTFE.They can use one Kind suitable can also be mixed with two or more.

For fluorinated resin particle, from the viewpoint of keeping the embeddability of fine wiring good, the volume of primary particle is average Preferably 5 μm or less, more preferable 4 μm or less, further preferred 3 μm or less of grain size.In addition, from making the good viewpoint of electrical characteristics go out Hair, preferably 0.005 μm or more of the volume average particle size of primary particle, more preferable 0.01 μm or more, it is further preferred 0.02 μm with On.

It should be noted that the arithmetic that " volume average particle size " in this specification refers to the particle diameter distribution of volume reference is put down Equal diameter.Volume average particle size can be for example measured by wet type laser diffraction scattering method.

The content of silica dioxide granule in silica covering fluorinated resin particle (A) is not particularly limited, from making flowing Property it is good from the perspective of, relative to the quality of fluorinated resin particle, preferably 0.001 mass % or more, more preferably 0.005 matter Measure % or more, further preferably 0.01 mass % or more.In addition, from the viewpoint of the electrical characteristics of performance fluorinated resin particle, Preferably 10 mass % or less, more preferably 5 mass % or less, further preferably 2 mass % or less.

For silica dioxide granule, as long as the volume average particle size of primary particle is average than the volume of aforementioned fluorinated resin particle Grain size is small, is just not particularly limited.Wherein, from the viewpoint of the electrical characteristics of performance fluororesin, the volume of primary particle is average Grain size is preferably 200nm or less, preferably 100nm or less, more preferable 70nm or less, further preferred 50nm or less.In addition, from making From the perspective of good fluidity, the preferred 0.3nm or more of volume average particle size of primary particle, more preferable 0.5nm or more, into one Walk preferred 1nm or more.

For silica covering fluorinated resin particle (A), from the viewpoint of keeping the embeddability of fine wiring good, once Preferably 5 μm or less of the volume average particle size of particle, more preferable 4 μm or less, it is further preferred 3 μm hereinafter, from fine wiring is made From the perspective of embeddability, dielectric constant and dielectric loss angle tangent are better, still more preferably 2 μm or less.In addition, from making From the perspective of electrical characteristics are good, preferably 0.005 μm or more of the volume average particle size of primary particle, more preferable 0.01 μm or more, Further preferred 0.02 μm or more.

Such silica covering fluorinated resin particle can also utilize commercially available product, such as can enumerate 0.5 μm of PTFE-YA (trade name), PTFE-YA4 (3.0 μm, trade name) (above, Admatechs Company Limited systems).

The content of silica covering fluorinated resin particle (A) in the resin combination of present embodiment does not limit especially It is fixed, from the viewpoint of keeping the electrical characteristics of resin combination good, relative to 100 matter of resin solid content in resin combination Measure part, be preferably set to 3 mass parts or more, more preferably be set as 5 mass parts or more, further preferably be set as 10 mass parts or more, into One step is preferably set to 15 mass parts or more, is further preferably set as 30 mass parts or more.In addition, from the good viewpoint of heat resistance is made Set out, relative to 100 mass parts of resin solid content in resin combination, be preferably set to it is 400 below mass part, more preferably set For it is 300 below mass part, be further preferably set as 200 below mass part, to be still more preferably set as 100 below mass part.

For the resin component (B) used in present embodiment, fluorinated resin particle is covered according to by using silica (A) electrical characteristics obtained from etc. and the solidfied material that is obtained using solidification required in the field of resin combination it is fire-retardant The characteristics such as property, heat resistance, thermal expansion character, can use various substances.Such as, it is desirable that it, can in the case of adaptation Enumerate epoxy resin, it is desirable that in the case of heat resistance, maleimide compound, cyanate esters, benzo can be enumerated Oxazine compounds, it is desirable that in the case of Thermocurable or photo-curable, the compound with ethylenically unsaturated group can be enumerated Deng further, it is also possible to use phenolic resin, oxetane resin etc..

In addition, they can use a kind of or suitable can also be mixed with two or more.

Hereinafter, being illustrated to the details of the resin component (B).

As maleimide compound, as long as the compound with more than one dimaleoyl imino in molecule, It is not particularly limited.As its concrete example, for example, can enumerate N-phenylmaleimide, N- hydroxyphenyl-maleimides, Bis- { 4- (the 4- maleimidephenoxies)-phenyl } propane of bis- (4- maleimide phenyls) methane, 2,2-, 4,4- diphenylmethyls Alkane bismaleimide, bis- (3,5- dimethyl -4- maleimide phenyls) methane, the bis- (Malaysias 3- ethyl -5- methyl -4- acyls Imines phenyl) methane, bis- (3,5- diethyl -4- maleimide phenyls) methane, phenylmethane maleimide, adjacent phenylene Bismaleimide, meta-phenylene bismaleimide, TOPOT 2,2′ p phenylenebis maleimide, adjacent phenylene dual-citraconic imide, Metaphenylene dual-citraconic imide, TOPOT 2,2′ p phenylenebis citraconimide, 2,2- bis- (4- (4- maleimidephenoxies)-phenyl) Propane, 3,3- dimethyl -5,5- diethyl -4,4- diphenyl methanes bismaleimide, 4- methyl-1s, 3- phenylene spans come Acid imide, 1,6- bismaleimide-(2,2,4- trimethyls) hexane, 4,4- diphenyl ethers bismaleimide, 4,4- hexichol Bis- (3- maleimidephenoxies) benzene of base sulfone bismaleimide, 1,3-, bis- (4- maleimidephenoxies) benzene of 1,3-, 4, Bis- [4- (the 4- citraconimides phenoxy group) phenyl] propane of 4- diphenyl methanes dual-citraconic imide, 2,2-, bis- (3,5- diformazans Base -4- citraconimides phenyl) methane, bis- (3- ethyl -5- methyl -4- citraconimides phenyl) methane, bis- (3,5- diethyls Base -4- citraconimides phenyl) methane, polyphenyl methylmethane maleimide, phenolic varnish type maleimide compound, biphenyl Malaysia shown in maleimide compound, following formula (5) shown in aralkyl-type maleimide compound, following formula (4) The prepolymer or maleimide compound of imide compound and these maleimide compounds and amine compounds it is pre- Polymers etc..

(in formula (4), multiple R₅Each independently represent hydrogen atom or methyl.n₁The integer for indicating 1 or more, preferably indicates 1 ~10 integer more preferably indicates 1~5 integer.).

(in formula (5), multiple R₆Each independently represent hydrogen atom or methyl.n₂The integer for indicating 1 or more, preferably indicates 1 ~5 integer.).

These maleimide compounds can also be used alone a kind or suitable for being mixed with two or more.Wherein, from resistance to It is hot it is excellent from the perspective of, preferably change shown in maleimide compound and previously described formula (5) shown in previously described formula (4) Close maleimide compound shown in object, more preferable previously described formula (4).As maleimide chemical combination shown in previously described formula (4) Object can also utilize commercially available product, such as can enumerate BMI-2300 (Daiwa Kasei Industry Co., Ltd.'s system).As previously described formula (5) maleimide compound shown in can also utilize commercially available product, such as can enumerate MIR-3000 (Japanese chemical drug strain formulas Commercial firm's system).

In the resin combination of present embodiment, the content of maleimide compound is not particularly limited, relative to tree 100 mass parts of resin solid content in oil/fat composition, the mass parts of preferably 0.01 mass parts~50, more preferably 0.02 mass Part~mass parts of 45 mass parts, further preferably 0.03 mass parts~20, still more preferably it is the mass of 0.1 mass parts~10 Part, further more preferably mass parts of 1 mass parts~7.By make maleimide compound content be above range in, To have the tendency that the heat resistance of solidfied material further increases.

As cyanate esters, replaced by least one cyanic acid ester group (cyanato group) as long as having for intramolecular Aromatic moiety resin, be just not particularly limited.

Such as general formula (6) compound represented can be enumerated.

(herein, in formula, Ar₁Indicate that phenyl ring, naphthalene nucleus or 2 phenyl ring carry out singly bounds and winner.Have a case that multiple Under, it each other can be identical or different.Ra each independently represent hydrogen atom, the alkyl of carbon number 1~6, carbon number 6~12 aryl, Group made of the alkoxy of carbon number 1~4, the alkyl of carbon number 1~6 are bonded with the aryl of carbon number 6~12.Aromatic rings in Ra can With with substituent group, Ar₁And the substituent group in Ra can select any position.P is indicated and Ar₁The quantity of the cyanic acid ester group of bonding, It is each independently 1~3 integer.Q is indicated and Ar₁The quantity of the Ra of bonding, Ar₁To be 6- when being 4-p when phenyl ring, being naphthalene nucleus It is 8-p when p, carrying out singly bound and winner for 2 phenyl ring.T indicates averaged repeating numbers, is 0~50 integer, cyanate chemical combination Object can be the mixture of the different compounds of t.Singly-bound, carbon number 1 are each independently represented in the case of multiple for X (hydrogen atom can be substituted by hetero atom to~50 divalent organic group.), the divalent organic group of nitrogen number 1~10 (such as-N-R- (R indicates organic group to N- herein.)), carbonyl (- CO-), carboxyl (- C (=O) O-), titanium dioxide carbonyl (- OC (=O) O-), sulphur Acyl group (- SO₂), any one in divalent sulphur atom or divalent oxygen atom.).

Alkyl in the Ra of general formula (6) can have straight or branched structure and cyclic structure (such as naphthenic base etc.) In arbitrary structures.

In addition, the hydrogen atom in aryl in alkyl and Ra in general formula (6) can be by the halogens such as fluorine atom, chlorine atom original The substitutions such as the alkoxies such as son, methoxyl group, phenoxy group or cyano.

As the concrete example of alkyl, can enumerate methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl, N-pentyl, 1- ethyl propyls, 2,2- dimethyl propyls, cyclopenta, hexyl, cyclohexyl and trifluoromethyl etc..

As the concrete example of aryl, phenyl, xylyl, dimethylbenzene methyl (mesityl group), naphthalene can be enumerated Base, Phenoxyphenyl, ethylphenyl, o-, m- or p- fluorophenyl, dichlorophenyl, dicyano phenyl, trifluorophenyl, methoxybenzene Base and o-, m- or p- tolyl etc..And then it is used as alkoxy, such as methoxyl group, ethyoxyl, propoxyl group, isopropyl oxygen can be enumerated Base, n-butoxy, isobutoxy and tert-butoxy etc..

The concrete example of divalent organic group as the carbon number 1~50 in the X of general formula (6) can enumerate methylene, sub- second The rings such as the alkylidenes such as base, trimethylene, propylidene, cyclopentylene, cyclohexylidene, trimethylcyclohexylene alkylidene, xenyl There is the divalent of aromatic rings to have for methylene, dimethylated methylene base-phenylene-dimethylated methylene base, fluorenes diyl and phthalide diyl etc. Machine group.Hydrogen atom in the divalent organic group can be by alkane such as the halogen atoms such as fluorine atom, chlorine atom, methoxyl group, phenoxy groups The substitutions such as oxygroup, cyano.

As the divalent organic group of the nitrogen number 1~10 in the X of general formula (6), group (R shown in-N-R-N- can be enumerated For organic group), it is imino group, polyimide-based etc..

In addition, the organic group as the X in general formula (6), such as the following general formula (7) or the following general formula (8) can be enumerated Shown in structure.

Herein, in formula, Ar₂It, each other can phase in the case of indicating that four base of benzene, four base of four base of naphthalene or biphenyl, u are 2 or more It is same or different.Rb, Rc, Rf and Rg each independently represent hydrogen atom, the alkyl of carbon number 1~6, the aryl of carbon number 6~12, three Methyl fluoride or aryl at least one phenolic hydroxyl group.Rd and Re is each independently selected from hydrogen atom, the alkyl of carbon number 1~6, carbon Any one of the aryl of number 6~12, the alkoxy of carbon number 1~4 or hydroxyl.U indicates 0~5 integer.

Herein, in formula, Ar₃It, each other can phase in the case of indicating that four base of benzene, four base of four base of naphthalene or biphenyl, v are 2 or more It is same or different.Ri and Rj each independently represents hydrogen atom, the alkyl of carbon number 1~6, the aryl of carbon number 6~12, benzyl, carbon number 1~4 alkoxy, hydroxyl, trifluoromethyl or aryl made of being replaced by least one cyanic acid ester group.V indicates 0~5 integer, It can be the mixture of the different compounds of v.

In turn, as the X in general formula (6), divalent group shown in following formula can be enumerated.

Herein, in formula, z indicates 4~7 integer.Rk each independently represents the alkyl of hydrogen atom or carbon number 1~6.

Ar as general formula (7)₂And the Ar of general formula (8)₃Concrete example, can enumerate 2 carbon atoms shown in general formula (7), Or 2 oxygen atoms bonds shown in general formula (8) are in 1,4 or 1,3 four bases of benzene, above-mentioned 2 carbon atoms or 2 oxygen atom keys Close four base of biphenyl and above-mentioned 2 carbon atoms or 2 in 4,4 ' positions, 2,4 ' positions, 2,2 ' positions, 2,3 ' positions, 3,3 ' positions or 3,4 ' positions Naphthalene four base of a oxygen atoms bond at 2,6,1,5,1,6,1,8,1,3,1,4 or 2,7.

Rb, Rc, Rd, Re, Rf and Rg of general formula (7) and alkyl in Ri, Rj of general formula (8) and aryl with it is above-mentioned logical Meaning in formula (6) is identical.

As the concrete example of cyanic acid ester group substituted aromatic compound shown in above-mentioned general formula (6), cyanate can be enumerated Base benzene, 1- cyanic acid ester group -2- methylbenzenes, 1- cyanic acid ester group -3- methylbenzenes or 1- cyanic acid ester group -4- methylbenzenes, 1- cyanates Base -2- methoxybenzenes, 1- cyanic acid ester group -3- methoxybenzenes or 1- cyanic acid ester group -4- methoxybenzenes, 1- cyanic acid ester groups -2,3- two Methylbenzene, 1- cyanic acid ester group -2,4- dimethyl benzenes, 1- cyanic acid ester group -2,5- dimethyl benzenes, 1- cyanic acid ester group -2,6- dimethyl Benzene, 1- cyanic acid ester group -3,4- dimethyl benzenes or 1- cyanic acid ester group -3,5- dimethyl benzenes, cyanate radical close ethylo benzene, cyanate radical closes fourth Base benzene, cyanate radical close octyl benzene, cyanate radical closes nonyl benzene, 2- (4- cyanatophenyls) -2- phenyl-propanes (4- α-cumyl phenol Cyanate), 1- cyanic acid ester group -4- cyclohexyl benzenes, 1- cyanic acid ester group -4- vinyl benzenes, 1- cyanic acid ester group -2- chlorobenzenes or 1- cyanogen Perester radical -3- chlorobenzenes, 1- cyanic acid ester group -2,6- dichloro-benzenes, 1- cyanic acid ester group -2- methyl -3- chlorobenzenes, cyanate radical close nitrobenzene, 1- cyanic acid ester group -4- nitro -2- ethylo benzenes, 1- cyanic acid ester group -2- methoxyl group -4- allyl benzenes (cyanate of eugenol), first Base (4- cyanatophenyls) sulfide, 1- cyanic acid ester group -3- trifluoromethylbenzenes, 4- cyanic acid ester groups biphenyl, 1- cyanic acid ester groups -2- Acetylbenzene or 1- cyanic acid ester group -4- acetylbenzenes, 4- cyanates benzaldehyde, 4- cyanate yl benzoic acids methyl esters, 4- cyanic acid Ester group phenol benzoate, 1- cyanic acid ester group -4- acetyl amino phenyls, 4- cyanic acid ester groups benzophenone, two uncles of 1- cyanic acid ester groups -2,6- Butyl benzene, 1,2- dicyanate bases benzene, 1,3- dicyanate bases benzene, 1,4- dicyanate bases benzene, 1,4- dicyanate base -2- uncles Butyl benzene, 1,4- dicyanate base -2,4- dimethyl benzenes, 1,4- dicyanate base -2,3,4- trimethylbenzenes, 1,3- dicyanates Base -2,4,6- trimethylbenzenes, 1,3- dicyanate base -5- methylbenzenes, 1- cyanic acid ester group naphthalenes or 2- cyanic acid ester groups naphthalene, 1- cyanates Base -4- methoxynaphthalenes, 2- cyanic acid ester group -6- methyl naphthalenes, 2- cyanic acid ester group -7- methoxynaphthalenes, 2,2 '-dicyanate bases -1,1 ' - Dinaphthalene, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7- dicyanate base dinaphthyl, 2,2 '-or 4,4 '-dicyan Perester radical biphenyl, 4,4 '-dicyanate base octafluorobiphenyls, 2,4 '-or 4,4 '-dicyanate base diphenyl methanes, bis- (4- cyanic acid Ester group -3,5- 3,5-dimethylphenyls) methane, bis- (4- cyanatophenyls) ethane of 1,1-, 1,1- bis- (4- cyanatophenyls) third Bis- (the 4- cyanic acid ester group -3- aminomethyl phenyls) propane of bis- (4- cyanatophenyls) propane of alkane, 2,2-, 2,2-, bis- (the 2- cyanic acid of 2,2- Ester group -5- xenyls) propane, bis- (4- cyanatophenyls) hexafluoropropane of 2,2-, bis- (the 4- cyanic acid ester group -3,5- diformazans of 2,2- Base phenyl) propane, bis- (4- cyanatophenyls) butane of 1,1-, bis- (4- cyanatophenyls) iso-butanes of 1,1-, the bis- (4- of 1,1- Cyanatophenyl) pentane, bis- (4- the cyanatophenyls) -3- methybutanes of 1,1-, bis- (4- the cyanatophenyls) -2- of 1,1- Bis- (4- the cyanatophenyls) -2,2- dimethylpropanes of methybutane, 1,1-, bis- (4- cyanatophenyls) butane of 2,2-, 2, Bis- (4- cyanatophenyls) pentanes of 2-, bis- (4- cyanatophenyls) hexanes of 2,2-, bis- (4- the cyanatophenyls) -3- of 2,2- Bis- (4- the cyanatophenyls) -4- methylpentanes of methybutane, 2,2-, bis- (4- the cyanatophenyls) -3,3- dimethyl of 2,2- Bis- (4- cyanatophenyls) hexanes of butane, 3,3-, bis- (4- cyanatophenyls) heptane of 3,3-, 3,3- are bis-, and (4- cyanate radicals close Phenyl) octane, bis- (4- the cyanatophenyls) -2- methylpentanes of 3,3-, bis- (4- the cyanatophenyls) -2- methyl of 3,3- oneself Bis- (4- the cyanatophenyls) -2,2- dimethyl pentanes of alkane, 3,3-, bis- (4- the cyanatophenyls) -3- methyl heptanes of 4,4-, 3, Bis- (4- the cyanatophenyls) -2- methyl heptanes of 3-, bis- (4- the cyanatophenyls) -2,2- dimethylhexanes of 3,3-, 3,3- are bis- Bis- (4- the cyanatophenyls) -2,2,4- trimethylpentanes of (4- cyanatophenyls) -2,4- dimethylhexanes, 3,3-, 2,2- Bis- (4- cyanatophenyls) -1,1,1,3,3,3- hexafluoropropane, bis- (4- cyanatophenyls) phenylmethanes, the bis- (4- of 1,1- Cyanatophenyl) -1- diphenylphosphino ethanes, bis- (4- cyanatophenyls) biphenyl methane, bis- (4- cyanatophenyls) rings of 1,1- Bis- (the 4- cyanic acid ester group -3- isopropyl phenyls) propane of bis- (4- cyanatophenyls) hexamethylenes of pentane, 1,1-, 2,2-, 1,1- are bis- (3- cyclohexyl -4- cyanatophenyls) hexamethylene, bis- (4- cyanatophenyls) diphenyl methanes, bis- (4- cyanate radicals close benzene Base) bis- [(4- cyanate radicals close benzene to 2- by -2,2- dichloroethylene, bis- [2- (4- the cyanatophenyls) -2- propyl] benzene of 1,3-, 1,4- Base) -2- propyl] benzene, bis- (4- the cyanatophenyls) -3,3,5- trimethyl-cyclohexanes of 1,1-, 4- [bis- (4- cyanatophenyls) Methyl] biphenyl, 4,4- dicyanate bases benzophenone, bis- (4- the cyanatophenyls) -2- propylene -1- ketone of 1,3-, bis- (4- cyanic acid Root close phenyl) ether, bis- (4- cyanatophenyls) sulfide, bis- (4- cyanatophenyls) sulfones, 4- cyanate yl benzoic acids -4- Cyanatophenyl ester (4- cyanatophenyl -4- cyanate yl benzoic acids ester), double-(4- cyanatophenyls) carbonic ester, Bis- (4- cyanatophenyls) adamantane of 1,3-, bis- (4- the cyanatophenyls) -5,7- dimethyladamantanes of 1,3-, 1,3- are bis- (3- methyl -4- cyanatophenyls) -5,7- dimethyladamantanes, bis- (4- cyanatophenyls) isobenzofurans -1 of 3,3- Bis- (4- cyanic acid ester group -3- aminomethyl phenyls) isobenzofuran -1 (3H) -one (o-cresols of (3H) -one (cyanate of phenolphthalein), 3,3- The cyanate of phthalein), 9,9 '-bis- (4- cyanatophenyls) fluorenes, bis- (the 4- cyanic acid ester group -3- aminomethyl phenyls) fluorenes of 9,9-, 9,9- it is bis- (2- cyanic acid ester group -5- xenyls) fluorenes, three (4- cyanatophenyls) methane, 1,1,1- tri- (4- cyanatophenyls) ethane, 1,1,3- tri- (4- cyanatophenyls) propane, α, α, α '-three (4- cyanatophenyls) -1- ethyl -4- cumenes, 1,1, (N- methyl -4- cyanate radicals close by 2,2- tetra- (4- cyanatophenyls) ethane, four (4- cyanatophenyls) methane, 2,4,6- tri- Anilino-) bis- (N- methyl -4- cyanate radicals close anilino-) -6- (methylphenylamine the base) -1,3,5- three of -1,3,5- triazines, 2,4- Piperazine, bis- (N-4- cyanic acid ester group -2- aminomethyl phenyls) -4,4 '-oxygen double phthalimide, bis- (N-3- cyanic acid ester group -4- methyl Phenyl) it is the double phthalimide of -4,4 '-oxygen, the double phthalimides of bis- (N-4- cyanatophenyls) -4,4 '-oxygen, double (N-4- cyanic acid ester group -2- aminomethyl phenyls) double phthalimides of -4,4 '-(hexafluoroisopropyli,ene bases), three (3,5- dimethyl - 4- cyanate radicals close benzyl) isocyanuric acid ester, bis- (4- cyanatophenyls) the benzyl first lactams of 2- phenyl -3,3-, 2- (4- methylbenzenes Base) bis- (4- cyanatophenyls) the benzyl first lactams of -3,3-, bis- (4- cyanic acid ester group -3- aminomethyl phenyls) the benzyl first of 2- phenyl -3,3- Bis- (4- cyanatophenyls) Indolin-2-ones of lactams, 1- methyl -3,3- and bis- (the 4- cyanate radicals conjunctions of 2- phenyl -3,3- Phenyl) Indolin-2-one and their prepolymer.

Wherein, from the viewpoint of heat resistance and dielectric constant, dielectric loss angle tangent are excellent, bis- (the 4- cyanogen of preferably 2,2- Acid group close phenyl) propane prepolymer.

These cyanate esters can be used alone or be mixed with two or more.

In addition, other concrete examples as above-mentioned general formula (6) compound represented, can enumerate phenol novolacs tree Fat and cresol novolac resin (by well known method, make phenol, alkyl substituted phenol or halogen-substituted phenol and formal The formaldehyde compounds such as woods, paraformaldehyde react and winner in an acidic solution), trisphenol novolac resin (make hydroxy benzenes first Aldehyde reacts and winner with phenol in the presence of acidic catalyst), fluorenes novolac resin (keep fluorenone compound and 9,9- bis- (hydroxyaryl) fluorenes class is reacted and winner in the presence of acidic catalyst), phenol aralkyl resin, cresols aralkyl resin, Naphthols aralkyl resin and biphenyl aralkyl resin (by well known method, make Ar₂-(CH₂Y)₂(Ar₂Indicate that phenyl, Y indicate Halogen atom.Below with it is same in this.) shown in such double halogenated methyl chemical combination objects and phenolic compound in acidic catalyst Or winner, make Ar without being reacted under catalyst₂-(CH₂OR)₂Shown such bis- (alkoxy methyl) compounds and phenols chemical combination Object reacts in the presence of acidic catalyst and winner or makes Ar₂-(CH₂OH)₂Shown such bis- (hydroxymethyl) compounds Reacted in the presence of acidic catalyst with phenolic compound and winner or make aromatic aldehyde compound, aralkyl compound and Phenolic compound polycondensation and winner), phenol be modified xylene formaldehyde resin (by well known method, make xylene formaldehyde resin with Phenolic compound reacts and winner in the presence of acidic catalyst), modified naphthalene formaldehyde resin (by well known method, make naphthalene Formaldehyde resin reacts and winner with hydroxyl substituted aromatic compound in the presence of acidic catalyst), phenol be modified two rings penta 2 Olefine resin, the phenolic resin with poly- naphthylene ether structure (by well known method, make have 2 or more phenolic hydroxyl groups in 1 molecule Polyhydroxy naphthalene compound in the presence of basic catalyst dehydrating condensation and winner) etc. phenolic resin, by as described above The esterification of method cyanic acid obtained from substance etc. and their prepolymer etc..It is not limited to these.These cyanate esters It can be used alone or be mixed with two or more.In addition, excellent from heat resistance, dielectric constant, dielectric loss angle tangent Aspect is set out, and is preferred by cyanate esters are used together shown in these cyanate esters and above-mentioned general formula (6).

Wherein, preferably phenol novolak type cyanate esters, naphthols aralkyl-type cyanate esters composition, biphenyl aralkyl Fundamental mode cyanate esters, naphthylene ether type cyanate esters, xylene resin type cyanate esters, adamantane framework type Cyanate esters, from heat resistance aspect, particularly preferred naphthols aralkyl-type cyanate esters composition.

It as the manufacturing method of these cyanate esters, is not particularly limited, well known method can be used.As institute The example of preparation method is stated, the hydroxy-containing compounds of acquisition or synthesis with desired skeleton can be enumerated, and pass through well known method pair The hydroxyl is modified and the method that carries out cyanic acid esterification.As the method for being esterified hydroxyl cyanic acid, such as Ian can be enumerated Hamerton, " Chemistry and Technology of Cyanate Ester Resins, " Blackie Academic＆ Method described in Professional.

Use the resin cured matter of these cyanate esters that there is glass transition temperature, low heat expansion, plating The excellent characteristic such as adaptation.

In the resin combination of present embodiment, the content of cyanate esters is not particularly limited, from heat resistance, is situated between From the perspective of electric constant, dielectric loss angle tangent are excellent, relative to 100 mass of resin solid content in resin combination Part, the mass parts of the mass parts of preferably 0.1 mass parts~50, more preferably 0.2 mass parts~40, further preferably 0.3 mass Part~20 mass parts, still more preferably it is the mass parts of 0.5 mass parts~10, the further mass of more preferably 1 mass parts~5 Part.

As epoxy resin, as long as the compound with 2 or more epoxy groups in 1 molecule, so that it may with suitable for using public affairs Its type is not particularly limited in the compound known.As its concrete example, such as bisphenol A type epoxy resin, bis-phenol can be enumerated E types epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type ring Oxygen resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, dimethylbenzene nobolak type epoxy tree Fat, multifunctional phenol-type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, naphthylene ether type ring Oxygen resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, 3 function phenol-type epoxy resins, 4 function phenol-type epoxy resins, Triglycidyl isocyanurate, glycidyl ester type epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolac type Epoxy resin, biphenyl phenolic resin varnish type epoxy resin, phenol aralkyl phenolic resin varnish type epoxy resin, naphthols aralkyl phenolic aldehyde are clear Paint shaped epoxy resin, aralkyl phenolic resin varnish type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthols aralkyl type epoxy tree Fat, dicyclopentadiene-type epoxy resin, polyol type epoxy resin, phosphorous epoxy resin, by glycidyl amine, butadiene etc. Compound made of double bond epoxidation, by the compound obtained by the reaction of hydroxyl organic siliconresin class and epoxychloropropane, And their halide.

Wherein, biphenyl aralkyl-type epoxy resin, naphthylene ether type epoxy, multifunctional phenol-type epoxy resin, naphthalene type Epoxy resin, brominated bisphenol a type epoxy resin are preferred in terms of anti-flammability, heat resistance.

These epoxy resin can be used alone, or suitable can also be mixed with two or more.

The content of epoxy resin is not particularly limited, relative to 100 mass parts of resin solid content in resin combination, The mass of the mass parts of the mass parts of preferably 0.1 mass parts~50, more preferably 0.2 mass parts~45, more preferably 5 mass parts~40 Part, be still more preferably the mass parts of 10 mass parts~25, further mass parts of more preferably 15 mass parts~25, most preferably For the mass parts of 12 mass parts~20.By make epoxy resin content be above range in, to have anti-flammability and heat resistance into The tendency that one step improves.

As phenolic resin, as long as the phenolic resin with 2 or more hydroxyls in 1 molecule, so that it may to use usual public affairs The phenolic resin known.Such as bisphenol A type phenolic resin, bisphenol E-type phenolic resin, bisphenol F type phenolic resin, bis-phenol can be enumerated S types phenolic resin, phenol resol resins, bisphenol A novolac type phenolic resin, glycidyl ester type phenolic resin, virtue Alkyl phenolic varnish-type phenolic resin, biphenyl aralkyl-type phenol resin, cresol novolak type phenolic resin, multifunctional phenolic aldehyde Resin, naphthol resin, naphthol novolac varnish gum, multifunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolac Type phenolic resin, phenol aralkyl type phenolic resin, naphthols aralkyl-type phenol resin, dicyclopentadiene type phenol resin, connection Benzene-type phenolic resin, ester ring type phenolic resin, polyol type phenolic resin, phosphorus containing phenolic resin, unsaturated alkyl containing polymerism Phenolic resin and hydroxyl organic siliconresin class etc., be not particularly limited.Among these phenolic resin, biphenyl aralkyl-type Phenolic resin, naphthols aralkyl-type phenol resin, phosphorus containing phenolic resin, hydroxyl organic siliconresin be excellent in terms of anti-flammability Choosing.These phenolic resin can be used alone, or suitable can also be mixed with two or more.

The content of phenolic resin is not particularly limited, relative to 100 mass of resin solid content in resin combination Part, the mass parts of the mass parts of preferably 0.1 mass parts~50, more preferably 0.2 mass parts~45, further preferably 0.3 mass Part~40 mass parts.By making the content of phenolic resin be in above range, to have the tendency that heat resistance further increases.

As oxetane resin, generally well-known oxetane resin can be used.Such as oxa- can be enumerated Cyclobutane, 2- methy oxetanes, 2,2- dimethyl oxygens azetidine, 3- methy oxetanes, 3,3- dimethyl oxa-s The alkyl such as cyclobutane oxetanes, 3- methyl -3- methoxies oxetanes, 3,3- bis- (trifluoromethyl) perfluor oxa- Bis- (chloromethyl) oxetanes of cyclobutane, 2- chloromethyls oxetanes, 3,3-, biphenyl type oxetanes, OXT-101 (Toagosei Co., Ltd's system, trade name), OXT-121 (Toagosei Co., Ltd's system, trade name) etc., do not limit especially System.These can also be used alone a kind or suitable for being mixed with two or more.

The content of oxetane resin is not particularly limited, relative to the resin solid content 100 in resin combination The mass parts of the mass parts of mass parts, preferably 0.1 mass parts~50, more preferably 0.2 mass parts~45, further preferably 0.3 The mass parts of mass parts~40.By making the content of oxetane resin be in above range, to there is heat resistance further to carry High tendency.

As benzoxazine compound, as long as the compound with 2 or more Er hydrogen benzoxazine rings in 1 molecule, Generally well-known compound can be used.Such as bisphenol A-type benzoxazine BA-BXZ (small western Chemical Co., Ltd. can be enumerated System, trade name), bisphenol-f type benzoxazine BF-BXZ (small westernization Co. Ltd. system, trade name), bisphenol S type benzoxazine BS-BXZ (small westernization Co. Ltd. system, trade name), phenolphthalein type benzoxazine etc., are not particularly limited.These can be used One kind suitable can also be mixed with two or more.

The content of benzoxazine compound is not particularly limited, relative to the resin solid content 100 in resin combination The mass parts of the mass parts of mass parts, preferably 0.1 mass parts~50, more preferably 0.2 mass parts~45, further preferably 0.3 The mass parts of mass parts~40.By making the content of benzoxazine compound be in above range, to there is heat resistance further to carry High tendency.

In the resin combination of present embodiment, in order to improve Thermocurable and based on the curability of active energy beam (such as photo-curable etc. based on ultraviolet light), can also be applied in combination the compound with ethylenically unsaturated group.This implementation As long as the compound with ethylenically unsaturated group used in mode is in 1 molecule with 1 or more ethylenically unsaturated group Compound, there is no particular limitation, such as the compound with (methyl) acryloyl group, vinyl can be enumerated.They It can use a kind of or suitable can also be mixed with two or more.

As the compound with (methyl) acryloyl group, (methyl) methyl acrylate, (methyl) acrylic acid can be enumerated Ethyl ester, (methyl) butyl acrylate, (methyl) lauryl acrylate, polyethylene glycol (methyl) acrylate, polyethylene glycol (first Base) acrylate monomethyl ether, (methyl) phenylethyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylate Ester, (methyl) benzyl acrylate, (methyl) tetrahydrofurfuryl acrylate, butanediol two (methyl) acrylate, two (first of hexylene glycol Base) acrylate, neopentyl glycol two (methyl) acrylate, nonanediol two (methyl) acrylate, ethylene glycol (glycol) two (methyl) acrylate, diethylidene two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, three (methyl) propylene Trimethylammonium isocyanuric acid ester, polypropylene glycol two (methyl) acrylate, adipic acid epoxy two (methyl) acrylate, bis-phenol Ethylene oxide two (methyl) acrylate, A Hydrogenated Bisphenol A ethylene oxide (methyl) acrylate, bis-phenol two (methyl) acrylate, 6-caprolactone modified hydroxyl neopentanoic acid neopentyl glycol two (methyl) acrylate, 6-caprolactone are modified dipentaerythritol six (methyl) Acrylate, 6-caprolactone are modified poly- (methyl) acrylate of dipentaerythritol, poly- (methyl) acrylate of dipentaerythritol, three Hydroxymethyl-propane three (methyl) acrylate, (methyl) acrylate of triethylol propane three and its ethylene oxide adduct, season Penta tetrol, three (methyl) acrylate and its ethylene oxide adduct, pentaerythrite four (methyl) acrylate, dipentaerythritol Six (methyl) acrylate and its ethylene oxide adduct etc..

In addition, can also enumerate same intramolecular has both (methyl) acryloyl group and the carbamate of urethane bond (methyl) esters of acrylic acid, similarly same intramolecular have both polyester (methyl) acrylic acid of (methyl) acryloyl group and ester bond The epoxy for being derived by epoxy resin and having both (methyl) acryloyl group (methyl) esters of acrylic acid, these keys are used in combination in ester Reactive oligomers etc..

Above-mentioned carbamate (methyl) esters of acrylic acid refer to hydroxyl (methyl) acrylate with polyisocyanates and The reactant of other alcohols used as needed.For example, making (methyl) Hydroxyethyl Acrylate, (methyl) dihydroxypropyl third (methyl) the hydroxyalkyl acrylates classes such as ester, (methyl) hydroxy butyl acrylate, single (methyl) glycerol acrylate, two (first Base) (methyl) glycerol acrylate class, pentaerythrite two (methyl) acrylate, the three (first of pentaerythrite such as glycerol acrylate Base) sugar alcohols (methyl) esters of acrylic acid such as acrylate, dipentaerythritol five (methyl) acrylate and, toluene diisocynate Ester, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, norbornene two Isocyanates, xylene diisocyanate, hydrogenated xylene diisocyanate, bicyclohexane methylene diisocyanate and it The reactions such as polyisocyanates such as isocyanuric acid ester, biuret reaction object, form carbamate (methyl) esters of acrylic acid.

Above-mentioned epoxy (methyl) esters of acrylic acid refers to the carboxylate of the compound and (methyl) acrylic acid with epoxy group Compound.Such as phenol novolak-type epoxy (methyl) acrylate, cresol novolak type epoxy (methyl) can be enumerated Acrylate, trihydroxy benzene methylmethane type ring oxygen (methyl) acrylate, bicyclopentadiene phenolic epoxy (methyl) acrylate, Bisphenol type epoxy (methyl) acrylate, bisphenol F type epoxy (methyl) acrylate, xenol type ring oxygen (methyl) acrylic acid Ester, bisphenol A novolac type ring oxygen (methyl) acrylate, epoxy containing naphthalene skeleton (methyl) acrylate, glyoxal type ring oxygen It is (methyl) acrylate, hetero ring type epoxy (methyl) acrylate and their anhydride modified epoxy (methyl) acrylate, preceding State general formula (1) compound represented etc..

In aforementioned formula (1), multiple R₁Each independently represent hydrogen atom or methyl.Wherein, from raising photocuring reaction Reactivity from the perspective of, preferably comprise hydrogen atom, more preferable R₁All hydrogen atoms.

Multiple R₂Each independently represent hydrogen atom or methyl.Wherein, from the viewpoint of the heat resistance for improving solidfied material, Preferably comprise methyl, more preferable R₂All methyl.

Multiple R₃Each independently represent substituent group or hydroxyl shown in substituent group, previously described formula (3) shown in previously described formula (2) Base.Wherein, from the viewpoint of improving heat resistance, hydroxyl is preferably comprised.In addition, in present embodiment, multiple R are used₃Middle packet Compound containing substituent group shown in previously described formula (2) is also preferred from the viewpoint of improving developability.In present embodiment, Use multiple R₃In the compound comprising substituent group shown in previously described formula (3) be also preferably from the viewpoint of improving heat resistance 's.In previously described formula (3), R₄Indicate hydrogen atom or methyl.Wherein, excellent from the viewpoint of the reactivity for improving photocuring reaction It is selected as hydrogen atom.

For multiple R₃, from the viewpoint of improving developability, preferably in whole R₃Substituent group in, previously described formula (2) institute The ratio of the substituent group shown be 20% or more and 85% or less, previously described formula (3) shown in substituent group ratio be 5% or more and 70% or less, the ratio of hydroxyl is 10% or more and 75% or less.

As aforementioned formula (1) compound represented, including any one of compound below (A1)~(A5) or more When, since the reactivity of photocuring reaction, the heat resistance of solidfied material and developability can be improved, preferably, more preferably at least Including compound (A1), even more preferably from comprising two or more in (A1)~(A5), further preferably including compound (A1) and change Close wantonly a kind or more in object (A2)~(A5).As compound (A), it is also preferred that including at least compound (A2) and (A3).

From the viewpoint of improving developability, the acid value of aforementioned formula (1) compound represented is 30mgKOH/g or more, The aspect further increased from developability, preferably 50mgKOH/g or more.In addition, from preventing from penetrating using active-energy From the perspective of being dissolved caused by developer solution after line solidification, the acid value of aforementioned formula (1) compound represented is 120mgKOH/ G hereinafter, from can further prevent dissolving aspect, preferably 110mgKOH/g or less.It should be noted that this implementation " acid value " in mode is indicated by being based on JIS K 0070：The value that 1992 method measures.

As anhydride modified epoxy acrylate, sour modified bisphenol F type epoxy acrylates can be enumerated.

These can use commercially available product, as aforementioned formula (1) compound represented, such as can enumerate Japanese chemical drug strain KAYARAD (registered trademark) ZCR-6001H, KAYARAD (registered trademark) ZCR-6002H, KAYARAD (registrations of formula commercial firm Trade mark) ZCR-6006H, KAYARAD (registered trademark) ZCR-6007H, KAYARAD (registered trademark) ZCA-601H (is above quotient The name of an article) etc..In addition, as sour modified bisphenol F type epoxy acrylates, Nippon Kayaku K. K can be enumerated KAYARAD (registered trademark) ZFR-1553H (trade name).

As the compound with vinyl, ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl can be enumerated The vinyl ethers such as base ether, ethylene glycol divinyl ether, 2 functionality phenylene ether oligomers with vinyl.As benzene second Alkenes can enumerate styrene, methyl styrene, ethyl styrene, divinylbenzene, α-methylstyrene and theirs is low Polymers etc..As other vinyl compounds, triallyl isocyanurate, three methallyl of isocyanuric acid, double can be enumerated Allyl nadikimide (bisallylnadiimide) etc..

Among these, it is preferably selected from by 2 functionality phenylene ether oligomers with vinyl, α-methylstyrene Oligomer, sour modified bisphenol F type rings oxygen (methyl) acrylate, aforementioned formula (1) compound represented, four (first of pentaerythrite Base) acrylate, dipentaerythritol six (methyl) acrylate, cresol novolak type epoxy (methyl) acrylate, bisphenol-A The group of type ring oxygen (methyl) acrylate, epoxy containing naphthalene skeleton (methyl) acrylate, diallyl nadikimide composition At least one of more than.For selected from by with vinyl 2 functionality phenylene ether oligomers, α-methylstyrene it is oligomeric Object, sour modified bisphenol F type rings oxygen (methyl) acrylate, six (first of aforementioned formula (1) compound represented and dipentaerythritol Base) acrylate composition one or more of group when, from obtaining good heat resistance, dielectric constant, dielectric loss angle tangent Aspect set out, be preferred.

It is required that in the case of Thermocurable, 2 functionality phenylene ether oligomers and/or Alpha-Methyl benzene second with vinyl Embeddability and solder heat resistance, dielectric constant, dielectric of the oligomer of alkene from progress heat cure well, good fine wiring It is preferred that the excellent aspect of loss angle tangent, which is set out,.It is required that in the case of photo-curable, including selecting free acid modified bisphenol F types What epoxy (methyl) acrylate, aforementioned formula (1) compound represented and dipentaerythritol six (methyl) acrylate formed More than at least one of group due to the embeddability and solder heat resistance and dielectric constant, dielectric loss angle of good fine wiring Tangent and developability are also excellent, therefore preferably, when using aforementioned formula (1) compound represented, and then excellent heat resistance, therefore More preferably.By the compound with ethylenically unsaturated group comprising such type, solidfied material to have it is resistance to The hot tendency further increased.

These compounds with ethylenically unsaturated group can use it is a kind of or can also suitable for be used in mixed way 2 kinds with On.In addition, these compounds with ethylenically unsaturated group can include the isomers such as constitutional isomer and stereoisomer, Can also proper combination use two or more different compound of structure each other.

The content of compound with ethylenically unsaturated group is not particularly limited, relative to the resin in resin combination The mass parts of the mass parts of 100 mass parts of solid constituent, preferably 0.1 mass parts~90, more preferably 0.2 mass parts~85.Pass through It is in above range, to have the tendency that solder heat resistance further increases that making, which has the compound of ethylenically unsaturated group,.It is special In the case of Thermocurable maybe being sought, from the embeddability and solder for carrying out heat cure well, obtaining good fine wiring It sets out in terms of heat resistance, dielectric constant, dielectric loss angle tangent, the content of the compound with ethylenically unsaturated group is opposite 100 mass parts of resin solid content in resin combination are preferably the mass parts of 5 mass parts~90, more preferably 7 mass parts ~85 mass parts, the further preferably mass parts of 10 mass parts~83.Furthermore, it desired in the case of photo-curable, it is good from obtaining It sets out in terms of the embeddability and solder heat resistance and dielectric constant, dielectric loss angle tangent and developability of good fine wiring, The content of compound with ethylenically unsaturated group is preferred relative to 100 mass parts of resin solid content in resin combination For the mass parts of 5 mass parts~90, the mass parts of more preferably 7 mass parts~85, the mass parts of further preferably 10 mass parts~80, Still more preferably it is the mass parts of 10 mass parts~73.

It can also contain in the range of not damaging the characteristic of present embodiment, in the resin combination of present embodiment and remove Silica covers the packing material (C) (hereinafter referred to as other packing materials (C)) other than fluorinated resin particle (A).Pass through combination Using other packing materials (C), the desired characteristic such as anti-flammability, heat resistance, thermal expansion character of solidfied material can be improved.

As other packing materials (C), as long as having insulating properties, there is no particular limitation, for example, in addition to natural titanium dioxide The titanium dioxides such as silicon, fused silica, synthetic silica, amorphous silica, aerosil, hollow silica The oxides such as silicon class, white carbon (white carbon), titanium white, zinc oxide, magnesia, zirconium oxide, boron nitride, aggregation nitridation Boron, silicon nitride, aluminium nitride, barium sulfate, aluminium hydroxide, heating aluminum hydroxide item for disposal (heat aluminium hydroxide, make A part for the crystallization water is reduced and winner), boehmite, the molybdenums chemical combination such as metal hydrates, molybdenum oxide, the zinc molybdate such as magnesium hydroxide Object, zinc borate, zinc stannate, aluminium oxide, clay, kaolin, talcum, calcined clay, roasting kaolin, fired talc, mica, E- Glass, A- glass, NE- glass, C- glass, L- glass, D- glass, S- glass, M- glass G20, staple glass fibre (include E glass The glass micro mists end such as glass, T glass, D glass, S glass, Q glass class.), hollow glass, the inorganic system such as globular glass filling material Other than material, can also enumerate the rubber powder of styrene type, butadiene-type, acrylic type etc., hud typed rubber powder and The packing material etc. of the organic systems such as silicone resin powder, silicone rubber powder, organosilicon composite powder.Wherein, preferably Selected from one or more of the group being made of silica, aluminium hydroxide, boehmite, magnesia, magnesium hydroxide and barium sulfate.It Can use it is a kind of or can also be suitable for being mixed with two or more.

These other packing materials (C) can be surface-treated with aftermentioned silane coupling agent etc..

Especially from the viewpoint of the heat resistance for improving solidfied material, preferred silica particularly preferably melts titanium dioxide Silicon.As the concrete example of silica, can enumerate SFP-130MC of Denka Company Limited etc., SC2050-MB, SC2050-MNU of Admatechs Company Limited, SC1050-MLE, YA010C-MFN, YA050C-MJA etc..

The average grain diameter of other packing materials (C) is not particularly limited, from the other filling materials made in resin combination From the perspective of the favorable dispersibility for expecting (C), preferably 15 μm or less in terms of median particle diameter.In addition, from making in resin combination From the perspective of the favorable dispersibility of other packing materials (C), preferably 0.005 μm or more of median particle diameter.

It should be noted that " median particle diameter " in this specification refers to, on the basis of a certain grain size, by the granularity of powder When being divided into 2 part, the number or quality of the particle of grain size larger side and the number or quality of grain size smaller side respectively occupy 50% grain size of all powders.Median particle diameter can be measured by wet type laser diffraction scattering method.

In the resin combination of present embodiment, the content of other packing materials (C) is not particularly limited, it is solid from improving From the perspective of the heat resistance of compound, relative to 100 mass parts of resin combination, it is preferably set to 5 mass parts or more, more preferably sets For more than 10 mass parts, be further preferably set as 20 mass parts or more.In addition, from the developability for making resin combination, fine cloth From the perspective of the embeddability of line is good, relative to 100 mass parts of resin combination, it is below mass part, more excellent to be preferably set to 400 Choosing is set as 350 below mass part, it is below mass part to be further preferably set as 300, be still more preferably set as 100 mass parts with Under.

In the range of not damaging the characteristic of present embodiment, the resin combination of present embodiment can also contain silane Coupling agent and/or Ricinate.By the way that silane coupling agent and/or Ricinate is applied in combination, packing material can be improved The desired characteristic such as dispersibility, the adhesive strength of resin and packing material.

As silane coupling agent, as long as to be generally filled with the silane coupling agent used in the surface treatment of material, do not have It is particularly limited to.As concrete example, such as the vinyl such as vinyltrimethoxysilane, vinyltriethoxysilane can be enumerated The amino silicones such as silane system, γ aminopropyltriethoxy silane, N- β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane Methane series；The epoxy silanes such as γ-glycidoxypropyltrime,hoxysilane system；γ-acryloyloxypropyltrimethoxysilane Equal acrylic-silanes system；N- β-(N- vinylbenzylaminoethyls)-gamma-amino propyl trimethoxy silicane hydrochloride, N- The cationic silicons methane series such as the hydrochloride of (vinyl benzene) -2- amino-ethyl -3- TSL 8330s；Phenyl silane The silane coupling agent etc. of system.These silane coupling agents can also be used alone a kind or proper combination uses two or more.

In the resin combination of present embodiment, the content of silane coupling agent is not particularly limited, usually relative to tree 100 mass parts of oil/fat composition are 0.1~10 mass parts.

As Ricinate, as long as the dispersion stabilizer of coating, is just not particularly limited.As concrete example, example Can such as enumerate BYK Japan KK DISPERBYK (registered trademark) -110,111,118,180,161, BYK (registrars Mark)-W996, the Ricinates such as W9010, W903.These Ricinates can be used alone, or can also be suitable It is mixed with two or more.

In the resin combination of present embodiment, the content of Ricinate is not particularly limited, usually relative to tree 100 mass parts of oil/fat composition are 0.1~10 mass parts.

In the range of not damaging the characteristic of present embodiment, the resin combination of present embodiment can also contain fire-retardant Agent (D).By the way that fire retardant (D) is applied in combination, it is desired that anti-flammability, heat resistance, thermal expansion character of solidfied material etc. can be improved Characteristic.

As fire retardant (D), as long as having anti-flammability, so that it may to use generally well-known fire retardant.Such as it can enumerate The brominations such as the double tetrabromo phthalimides of brominated polycarbonate, decabromodiphenylethane, 4,4- '-dibromobiphenyls, ethylene organise Object is closed, is not particularly limited.These can be used alone, or suitable can also be mixed with two or more.

In the resin combination of present embodiment, the content of fire retardant (D) is not particularly limited, usually relative to resin 100 mass parts of resin combination in composition are 0.1~10 mass parts, preferably 1~10 mass parts.

In the resin combination of present embodiment, the resin component (maleimide using the energy photocuring such as ultraviolet light is used Amine compounds, epoxy resin, the compound with ethylenically unsaturated group, phenolic resin, oxetane resin etc.) as tree It,, can be in the range of not damaging the characteristic of present embodiment in order to improve its photo-curable in the case of fat ingredient (B) Contain trigger for optical solidification (E).

It as trigger for optical solidification (E), is not particularly limited, can use commonly used in Photocurable resin composition Well known trigger for optical solidification in field.

Such as the benzene such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether can be enumerated Acyloin class, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, chloro benzoyl peroxide, diperoxy neighbour's benzene Organic peroxide, acetophenone illustrated by dicarboxylate etc., 2,2- diethoxy -2- phenyl acetophenones, 2,2- bis- Ethyoxyl -2- phenyl acetophenones, 1,1- dichloroacetophenones, 2- hydroxy-2-methyls-phenyl-propane -1- ketone, diethoxybenzene second The acetophenones such as ketone, 1- hydroxycyclohexylphenylketones, 2- methyl-1s-[4- (methyl thio) phenyl] -2- morpholinoes-propane -1- ketone Anthraquinones, 2,4- diethyl thioxanthones, the 2- such as class, 2- ethyl hydrazine, 2- tertiary butyls anthraquinone, 2- chloroanthraquinones, 2- amyl anthraquinones are different Ketals class, two such as the thioxanthene ketone class such as propyl thioxanthones, 2-chlorothioxanthone, acetophenone dimethyl ketal, benzil dimethyl ketal Benzophenones, the 2,4,6- tri- such as Benzophenone, 4- benzoyls -4 '-methyldiphenyl thioether, 4,4 '-bis- methylamino benzophenone Phosphinoxides, 1- [4- (the benzene sulphur such as toluyl diphenyl phosphine oxide, bis- (2,4,6- trimethylbenzoyls)-phenyl phosphine oxides Base) -1,2- octanediones 2- (O- benzoyls oxime)] etc. free radical types trigger for optical solidification, the p-methoxyphenyl weight such as oximes esters Nitrogen fluorinated phosphonic acid salt, N, the lewis acidic diazol such as N- diethylamino phenyldiazonium hexafluorophosphonates, diphenyl iodine hexafluoro Lewis acidic salt compounded of iodine, triphenylsulfonium hexafluorophosphonate, the triphenylsulfonium hexafluoros such as phosphonate, diphenyl iodine hexafluoro antimonate The Louis Suan such as the lewis acidic sulfonium salt such as stibate, triphenyl phosphonium hexafluoro antimonate phosphonium salts, other halides, triazine system The cationic systems Photoepolymerizationinitiater initiaters such as initiator, borate-based initiator and other photoacid generators.

Wherein, from the reactivity suitable for multilayer board purposes, the viewpoint high to the reliability of metallic conductor Set out, preferably 2- benzyls -2- dimethylaminos -1- (4- morphlinophenyls)-butanone -1 (BASF Japan Ltd. systems, Irgacure (registered trademark) 369) etc. acetophenones free radical type trigger for optical solidification.

These trigger for optical solidification (E) can be used alone or can also be suitable for being mixed with two or more, can group It closes using free base system and cationic system both initiators.

The content of trigger for optical solidification (E) in the resin combination of present embodiment is not particularly limited, from utilization Active energy beam makes resin combination fully cure, improve heat resistance from the perspective of, relative to the tree in resin combination 100 mass parts of fat solid constituent are preferably set to 0.1 mass parts or more, are more preferably set as 0.2 mass parts or more, are further preferred It is set as 0.3 mass parts or more, is still more preferably set as 1 mass parts or more.In addition, heat cure, drop after hindering photocuring From the perspective of low heat resistant, relative to 100 mass parts of resin solid content in resin combination, it is preferably set to 30 mass parts Below, more preferably it is set as 25 below mass part, to be further preferably set as 20 below mass part, is still more preferably set as 10 mass Part or less.

In the resin combination of present embodiment, can also be combined in the range of not damaging the characteristic of present embodiment makes Use thermosetting accelerator.It as thermosetting accelerator, is not particularly limited, such as benzoyl peroxide, peroxidating can be enumerated Organic mistake illustrated by lauroyl, acetyl peroxide, chloro benzoyl peroxide, diperoxy phthalic acid di tert butyl carbonate etc. Oxide；The azo-compounds such as the double nitriles of azo；N, N- dimethyl benzylamine, N, accelerine, N, N- dimethyl toluidines, 2- N-ethylaniline base ethyl alcohol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethyl fourth The tertiary amines such as diamines, N- methyl piperidines；The phenols such as phenol, xylenol, cresols, resorcinol, catechol；Lead naphthenate, tristearin The acetylacetonate of lead plumbate, zinc naphthenate, zinc octoate, oleic acid tin, dibutyitin maleate, manganese naphthenate, cobalt naphthenate, iron Equal organic metal salts；These organic metal salts are dissolved in substance made of the hydroxy-containing compounds such as phenol, bis-phenol；Stannic chloride, The inorganic metal salts such as zinc chloride, aluminium chloride；The organo-tin compounds such as dioctyl tin oxide, other tin alkyls, alkyl-tin oxide；1, Imidazolium compounds such as 2- methylimidazoles, 1- benzyl -2- phenylimidazoles, 2,4,5- triphenylimidazolyls etc..

These thermosetting accelerators can be used alone, or suitable can also be mixed with two or more.

In the resin combination of present embodiment, the content of thermosetting accelerator is not particularly limited, usually relative to 100 mass parts of resin combination in resin combination are 0.1~10 mass parts.

Solvent can be contained in the resin combination of present embodiment as needed.If, can for example, using organic solvent Enough adjust the viscosity when preparation of resin combination.For the type of solvent, as long as can be by one of the resin in resin combination Partly or entirely dissolving, is just not particularly limited.As its concrete example, it is not particularly limited, such as acetone, first and second can be enumerated The ketones such as ketone, methyl cellosolve；Toluene, dimethylbenzene etc. are aromatic hydrocarbon；The amides such as dimethylformamide；Propylene glycol monomethyl ether And its acetic acid esters.

These organic solvents can be used alone, or suitable can also be mixed with two or more.

It can also be applied in combination in the range for not damaging the characteristic of present embodiment in the resin combination of present embodiment It is unrequited so far go out heat-curing resin, thermoplastic resin and its oligomer, the various macromolecule chemical combination such as elastomer class Object；It is unrequited so far go out anti-flammability compound；Additive etc..As long as these are usually used substance, do not have It is particularly limited to.For example, for the compound of anti-flammability, the nitrogenous compounds such as melamine, benzoguanamine can be enumerated, contain oxazines The phosphate compound of cycle compound and phosphorus series compound, aromatic condensation phosphate, condensed phosphoric acid esters containing halogen etc..As Additive can enumerate ultra-violet absorber, antioxidant, fluorescent whitening agent, photosensitizer, dyestuff, pigment, thickener, lubrication Agent, antifoaming agent, surface conditioner, gloss agent, polymerization inhibitor etc..These ingredients can be used alone, or can also be suitable for mixed It closes and uses two or more.

In the resin combination of present embodiment, the content of other ingredients is not particularly limited, usually relative to resin 100 mass parts of composition are respectively 0.1~10 mass parts.

The resin combination of present embodiment by silica by covering fluorinated resin particle (A), resin component (B) and root It is prepared according to the suitable mixing of the above-mentioned other any ingredients used it is expected.After the resin combination of present embodiment can be with making The form of varnish when the prepreg and resin sheet of the present embodiment stated is suitable for use.

The manufacturing method of the resin combination of present embodiment is not particularly limited, for example, can enumerate by it is above-mentioned respectively at Divide the method for being compounded successively into solvent and being fully stirred.

In the manufacture of resin combination, the public affairs for making each ingredient equably dissolve or disperse can be carried out as needed The processing (stirring, mixing, mixing process etc.) known.Specifically, by using stirring with stirring capacity appropriate is accompanied with The stirred tank for mixing machine is stirred decentralized processing, can improve silica covering fluorinated resin particle (A) in resin combination Dispersibility.Above-mentioned stirring, mixing, mixing process can use the stirring such as ultrasonic homogenizer for the purpose of dispersion The mixing of the device or revolution or rotation type for the purpose of mixing such as device, triple-roller mill, ball mill, ball mill, sand mill fills It the well known device such as sets suitably to carry out.In addition, in the preparation of the resin combination of present embodiment, can make as needed Use organic solvent.For the type of organic solvent, as long as can be by the fat-solvent type of tree in resin combination, without spy It does not limit, concrete example is as described above.

The resin combination of present embodiment can be used for needing the purposes of the resin combination of insulating properties, not limit especially It is fixed, it can be used for the insulating resin sheets such as photosensitive film, the photosensitive film with supporter, prepreg, circuit board (plywood Purposes, multilayer board purposes etc.), solder resist, underfill, chip grafting material, semiconductor-encapsulating material, fill out The purposes such as hole resin, component embedded resin.Wherein it is possible to be preferably used as the insulating layer resin combination of multilayer board Object, solder resist.

The prepreg of the present embodiment is make the resin combination of above-mentioned present embodiment infiltrate or be coated on base material to form 's.As long as the manufacturing method of prepreg is that the resin combination of present embodiment and substrate combination are manufactured the side of prepreg Method is just not particularly limited.Specifically, can be by making the resin combination of present embodiment infiltrate or be coated on base material Afterwards, 2~15 minutes or so methods etc. are made it dry at 120~220 DEG C makes its semi-solid preparation, thus manufactures present embodiment Prepreg.At this point, resin combination (includes packing material relative to the adhesion amount of base material, i.e. resin combination object amount.) relative to The total amount of prepreg after semi-solid preparation is preferably the range of 20~99 mass %.

The base material used when as the prepreg for manufacturing present embodiment can use institute in various printed circuit board materials Well known base material.Such as can enumerate E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass, The organic fibers such as inorfil, polyimides, polyamide, the polyester in addition to glass such as the glass fibres such as globular glass, quartz, The woven fabrics such as liquid crystal polyester, are not limited to these.Shape as base material, it is known to woven fabric, non-woven fabrics, rove, short glass fiber felt, Surface felt etc. can be any one.Base material can be used alone or two or more is applied in combination.In addition, to the thickness of base material Degree is not particularly limited, the preferred range of 0.01~0.2mm when being plywood purposes, real from the viewpoint of dimensional stability Super fibrillation process is applied, the woven fabric of eyelet plugging handling is particularly suitable for.In turn, it has been carried out at epoxy silane with silane coupling agent etc. The glass woven fabric of the surface treatments such as reason, aminosilane-treated is preferred from the viewpoint of moisture absorption heat resistance.In addition, liquid crystal is poly- Ester woven fabric is preferred from electrical characteristics aspect.

The clad with metal foil plywood of present embodiment is that metal foil is configured at least 1 or more above-mentioned prepreg overlapping In its one or two sides and carry out it is cascading into shape made of.Specifically, can be by by one or more prepreg above-mentioned Overlapping configures copper, the metal foils such as aluminium in its one or two sides, carries out cascading into shape make.As long as metal foil used herein For metal foil used in printed circuit board material, there is no particular limitation, the copper foils such as preferred rolled copper foil, electrolytic copper foil.Separately Outside, the thickness of metal foil is not particularly limited, preferably 2~70 μm, 3~35 μm more preferable.As molding condition, can apply Common printed circuit board plywood and multiple-plate method.For example, can be by using multistage press, multi-stage vacuum pressure Machine processed, progressive forming machine, autoclave forming machine etc., 180~350 DEG C of temperature, 100~300 minutes heating times, face pressure 20~ 100kg/cm²It is lower carry out it is cascading into shape come manufacture the present invention clad with metal foil plywood.Alternatively, it is also possible to by above-mentioned prepreg and The wiring plate group of the internal layer separately made is merged into that row is cascading into shape to be made multi-layer board.As multi-layer board manufacturing method, For example, can be made as got off：35 μm of copper foil is configured on the two sides of 1 above-mentioned prepreg, is laminated under these conditions After forming, internal layer circuit is formed, Darkening process is implemented to the circuit and forms inner layer circuit board, thereafter, by the inner layer circuit board Be alternately arranged with opening 1 with above-mentioned prepreg 1, so outermost layer configure copper foil, under these conditions, preferably under vacuum into Row is cascading into shape, thus makes multi-layer board.

On the other hand, the resin sheet of present embodiment can be by that will be such that the resin combination of above-mentioned present embodiment dissolves Made of solvent solution coating is obtained in supporter and being dried.As supporter used herein, such as can enumerate It is total to go out polyethylene film, polypropylene film, polycarbonate film, pet film, ethylene tetrafluoroethylene Homopolymer film and the organic systems such as mould release film, Kapton made of the surface coated release agent of these films The supporter of the plates such as the conductor foils such as film substrate, copper foil, aluminium foil, glass plate, SUS plates, FRP, is not particularly limited.

In turn, in the resin sheet of present embodiment, resin composition layer can be protected by protective film.

By protecting resin composition layer side with protective film, dust etc. can be prevented in the attached of resin combination layer surface It, damage.As protective film, the film being made of material same as above-mentioned resin film can be used.It is thin to protecting The thickness of film is not particularly limited, preferably 1 μm~50 μm of range, more preferably 5 μm~40 μm of range.Thickness is less than 1 μ When m, have the tendency that the treatability of protective film reduces, if more than 50 μm, it is cheapness poor to have the tendency that.It should be noted that For protective film, the bonding force of the bonding force of preferred resin composition layer and protective film than resin composition layer and supporter It is small.

As coating method, such as the following methods can be enumerated：With bar coater, die coating machine, scraper, Baker applicators etc., The resin combination of present embodiment will be made to be dissolved in solution coating made of solvent on supporter, thus make supporter with The laminates that resin sheet is integrally formed.Alternatively, it is also possible to after the drying, supporter be removed or is etched from laminates, by The single-layer sheet for being individually for resin sheet is made in this.It should be noted that the resin combination of above-mentioned present embodiment can also will be made It is dissolved in solution made of solvent to be supplied in the mold with sheet die cavity and be dried etc. and be configured to sheet, thus not Using supporter obtain single-layer sheet.

It should be noted that in the making of the resin sheet (single layer or laminates) of present embodiment, when to removal solvent Drying condition be not particularly limited, if low temperature, then solvent is easy to remain in resin combination, if high temperature, then resin Composition can cure, therefore preferably 1~90 minute at a temperature of 20 DEG C~200 DEG C.In addition, the resin sheet of present embodiment The thickness of the resin layer of (single layer or laminates) can be by the solution of the resin combination of present embodiment concentration and coating Thickness is adjusted, and is not particularly limited, if usually coating thickness thickens, solvent is easy residual when drying, therefore preferably 0.1~500 μm.

The clad with metal foil plywood and resin sheet of present embodiment can be suitable for using as printed circuit board.Printed circuit Plate can be manufactured conventionally, its manufacturing method is not particularly limited.Hereinafter, showing to have used metal-clad An example of the manufacturing method of the printed circuit board of lamination.First, prepare the clad with metal foil plywood such as above-mentioned copper-clad laminated board.It connects It, etching process is implemented to the surface of clad with metal foil plywood, carries out the formation of internal layer circuit, makes internal substrate.It is interior to this The internal layer circuit surface of laminar substrate carries out the surface treatment for improving adhesive strength as needed, then in its internal layer circuit table The above-mentioned prepreg of required number is overlapped by face, and then the metal foil of outer circuit is laminated on the outside, carries out heating pressurization And it carries out integrally formed.In this way operate, manufacture be formed between internal layer circuit and the metal foil of outer circuit base material and by The multilayer laminate of the insulating layer of the solidfied material of hot curing resin composition.Then, to the plywood of the multilayer implement through-hole, After the drilling processing of via hole, the wall surface in the hole, which is formed, makes the gold-plated of the metal foil of internal layer circuit and outer circuit conducting Belong to overlay film, and then etching process is implemented to the metal foil of outer circuit and forms outer circuit, to manufacture printed circuit board.

The printed circuit board obtained in above-mentioned Production Example has insulating layer and is formed in the conductor on the surface of the insulating layer Layer, insulating layer are the composition of the resin combination comprising above-mentioned present embodiment.That is, prepreg (the base of above-mentioned present embodiment Material and infiltration or be coated on the base material present embodiment resin combination), the stacking of the clad with metal foil of above-mentioned present embodiment The layer (layer formed by the resin combination of the present invention) of the resin combination of plate is by the resin combination comprising present embodiment Insulating layer constitute.

Hereinafter, showing to have used an example of the manufacturing method of the printed circuit board of resin sheet.The resin sheet of present embodiment It can be suitable for use as the interlayer insulating film of printed circuit board, 1 or more above-mentioned resin sheet can be overlapped and be cured and It arrives.It can specifically be manufactured by the following method.

One or two sides by the resin composition layer side of the resin sheet of present embodiment in circuit board shapes.As at Profile bar part can apply common printed circuit board plywood and multiple-plate method, can also be shaped by vacuum lamination. As circuit board, such as glass epoxy substrate, metal substrate, ceramic substrate, silicon substrate, semiconductor sealing resin can be enumerated Substrate, polyester substrate, polyimide substrate, BT resin substrates, thermohardening type polyphenylene ether substrate etc..It should be noted that Herein circuit board refer to substrate as described above one or two sides be formed with carry out pattern be process conductor layer (electricity Road) substrate.In addition, in the multilayer board made of conductor layer and insulating layer is alternately laminated, the multi-sheet printed electricity The substrate of the outermost conductor layer (circuit) that pattern processing has been carried out as one or two sides of road plate is also included within this place In the circuit board said.It should be noted that can be implemented in advance to conductor layer surface by Darkening process, copper etching etc. coarse Change is handled.In molding procedure, in the case where resin sheet has protective film, after protective film stripping removal, according to It needs to preheat resin sheet and circuit board, circuit base is crimped on when being pressurizeed and being heated to resin composition layer Plate.In the resin sheet of present embodiment, suitable the side for being laminated to circuit board under reduced pressure by vacuum layer platen press can be used Method.

Condition to being laminated process is not particularly limited, such as is preferably, preferred that will crimp temperature (laminating temperature) It is set as 50 DEG C~140 DEG C, crimping pressure is preferably set to 1kgf/cm²~15kgf/cm², will crimping the time be preferably set to 5 seconds ~300 seconds, air pressure is set as under 20mmHg decompressions below being laminated.In addition, lamination process can be intermittent, Or the continous way using roller.Vacuum layer platen press can be carried out using commercially available vacuum laminator.As commercially available true Dead level press, such as 2 rank lamination laminating machine of Nikko-Materials Co., Ltd.s system can be enumerated etc..

Hole machined processing is implemented to form via hole, through-hole etc..Hole machined processing uses NC drill bits, titanium dioxide Wantonly a kind in method well known to carbon laser, UV laser, YAG laser, plasma etc. or combine two or more as needed and It carries out.In the case that resin sheet is Photocurable resin composition, hole machined processing can also be implemented by exposing, developing.

Implement before hole machined processing or as needed post-bake process after processing and forms insulating layer (solidfied material).As rear Roasting procedure, the heating process etc. that the ultraviolet light irradiation process using high-pressure sodium lamp can be enumerated, used cleaning oven.It is shining In the case of penetrating ultraviolet light, its exposure can be adjusted as needed, such as can be with 0.05J/cm²~10J/cm²The photograph of left and right The amount of penetrating is irradiated.In addition, the condition of heating is carried out according to type, content of the resin component in resin combination etc. suitable for choosing Select, preferably at 150 DEG C~220 DEG C 20 minutes~180 minutes ranges, more preferably 30 minutes at 160 DEG C~200 DEG C ~150 minutes ranges are selected.

In the case where surface of insulating layer has conductor layer, the wall surface in hole, which is formed, makes internal layer circuit and outer circuit The plating of metal foil conducting is metal film coated, and then to the metal foil of outer circuit implementation etching process to form outer circuit, Thus printed circuit board is manufactured.

In the case where surface of insulating layer does not have conductor layer, then, insulating layer table is plated on by dry type plating or wet type Face forms conductor layer.As dry type plating, method well known to vapour deposition method, sputtering method, ion plating method etc. can be used.For vapor deposition Method (vacuum vapour deposition), such as supporter can be put into vacuum tank, METAL HEATING PROCESS is evaporated, thus on the insulating layer into Row metal film is formed.For sputtering method, such as supporter can also be put into vacuum tank, import the nonactive gas such as argon gas Body applies DC voltage, so that ionized non-active gas is hit target metal, is carried out on the insulating layer by knocking-on metal Metal film is formed.

In the case of wet type plating, carried out successively at the swelling using swelling solution by the surface of the insulating layer to formation Reason, the roughening treatment using oxidant and the neutralisation treatment using neutralizer, are roughened surface of insulating layer.Using molten The swelling treatment of swollen liquid is carried out by making insulating layer be impregnated in swelling solution at 50 DEG C~80 DEG C 1 minute~20 minutes.As Swelling solution can enumerate aqueous slkali, as the aqueous slkali, can enumerate sodium hydroxide solution, potassium hydroxide solution etc..As city The swelling solution sold, such as APPDES (registered trademark) MDS-37 etc. that C. Uyemura ＆ Co Ltd can be enumerated.

Using the roughening treatment of oxidant oxidizing agent solution is impregnated at 60 DEG C~80 DEG C 5 minutes by making insulating layer It carries out within~30 minutes.As oxidant, such as it can enumerate and potassium permanganate, sodium permanganate are dissolved in the water-soluble of sodium hydroxide Alkaline permanganic acid solution, bichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid etc. made of liquid.In addition, alkaline permanganic acid solution In the concentration of permanganate be preferably set to 5 mass of mass %~10 %.As commercially available oxidant, such as village can be enumerated The alkalinity permanganic acid solution such as Industrial Co., Ltd APPDES (registered trademark) MDE-40, APPDES (registered trademark) ELC-SH. It is carried out using the neutralisation treatment of neutralizer by being impregnated in neutralizer at 30 DEG C~50 DEG C 1 minute~10 minutes.As in And liquid, the aqueous solution of preferred acidic can enumerate the APPDES (registered trademark) of C. Uyemura ＆ Co Ltd as commercially available product MDN-62。

Then, combinatorial chemistry plates and is electroplated and forms conductor layer.Alternatively, it is also possible to form opposite with conductor layer pattern resist Coating only forms conductor layer by chemical plating.As the method that pattern thereafter is formed, subraction can be used for example, partly add Addition etc..

The semiconductor device of present embodiment has the interlayer insulating film of the resin combination comprising present embodiment, specifically For can be manufactured by the following method.It can be pacified by the conducting position of the multilayer board in present embodiment Semiconductor chip is filled to manufacture semiconductor device.Herein, conducting position refers to the transmission electric signal in multilayer board Position, position can be surface, or embedded position.In addition, as long as semiconductor chip is using semiconductor as material Circuit element, be just not particularly limited.

For manufacture present embodiment semiconductor device when semiconductor chip installation method, as long as semiconductor chip It can effectively play a role, there is no particular limitation, specifically, wire bonding installation method, flip-chip peace can be enumerated Dress method, installation method, the installation method using anisotropic conducting film (ACF), profit using bumpless increasing layer (BBUL) With the installation method etc. of non-conductive film (NCF).

In addition, by the way that the resin sheet of present embodiment is laminated to semiconductor chip, semiconductor device can be also manufactured.Layer After pressure, method same as multilayer board above-mentioned can be used to manufacture.

Embodiment

Hereinafter, by synthesis example, embodiment, more specifically the present invention will be described, but the present invention is not by these embodiments Any restriction.

(synthesis example 1)

(synthesis of cyanate esters)

1- naphthols aralkyl resin (Nippon Steel ＆ Sumitomo Metal Corporation's system) 300g is set (to carry out OH bases to be scaled 1.28mol) and triethylamine 194.6g (1.92mol) (being 1.5mol relative to hydroxyl 1mol) is dissolved in dichloromethane 1800g, will It is as solution 1.

By cyanogen chloride 125.9g (2.05mol) (being 1.6mol relative to hydroxyl 1mol), dichloromethane 293.8g, 36% salt Sour 194.5g (1.92mol) (1 mole is 1.5 moles relative to hydroxyl), water 1205.9g under stiring, side remain liquid temperature -2 ~-0.5 DEG C, the 30 minutes injection solution 1 in side.After solution 1 injects, after stirring 30 minutes at the same temperature, with 10 points Clock injection makes triethylamine 65g (0.64mol) (being 0.5mol relative to hydroxyl 1mol) be dissolved in solution made of dichloromethane 65g (solution 2).After solution 2 injects, stirs 30 minutes at the same temperature, reaction is made to terminate.

Thereafter reaction solution is stood, by organic phase and aqueous phase separation.Obtained organic phase is cleaned 5 times with water 1300g.The The conductivity of the waste water of 5 washings is 5 μ S/cm, it is thus identified that：By using the cleaning of water, the ionic compound quilt to be removed Fully removal.

Organic phase after washing is concentrated under reduced pressure, finally carries out being concentrated and dried solidification in 1 hour at 90 DEG C, obtains mesh Mark cyanate esters (SNCN) (orange gummy object) 331g of naphthols aralkyl-type.The matter average molecular weight Mw of gained SNCN is 600.In addition, the IR spectrums of SNCN show 2250cm^-1The absorption of (cyanic acid ester group), also, the absorption of hydroxyl is not shown.

(synthesis example 2)

(synthesis of the 2 functionality phenylene ether oligomer bodies with vinyl)

With agitating device, thermometer, air leading-in conduit, baffle 12L longitudinal reaction device in put into CuBr 23.88g (17.4mmol), N, N '-di-t-butyl ethylenediamine 0.75g (4.4mmol), normal-butyl dimethylamine 28.04g (277.6mmol), toluene 2600g is stirred at 40 DEG C of reaction temperature, and lateral dominance is prepared into nitrogen and air is mixed The mixed gas of oxygen concentration 8% was bubbled with 5.2L/ minutes flow velocitys, and side was added dropwise with 230 minutes and is dissolved in 2300g first in advance The 2,2 ' of alcohol, -4,4 '-glycol 129.3g (0.48mol) of 3,3 ', 5,5 '-hexamethyls-(1,1 '-xenol), 2,6- dimethyl benzenes Phenol 233.7g (1.92mol), 2,3,6- pseudocuminols 64.9g (0.48mol), N, N '-di-t-butyl ethylenediamines 0.51g The mixed solution of (2.9mmol), normal-butyl dimethylamine 10.90g (108.0mmol), and be stirred.After completion of dropwise addition, it is added Water 1500g dissolved with tetrasodium ethylenediamine tetraacetate 19.89g (52.3mmol), makes reaction stop.Water layer and organic layer are carried out Liquid separation is cleaned organic layer with the aqueous hydrochloric acid solution of 1N, is then cleaned with pure water.Acquired solution is concentrated into evaporator 50wt% obtains the toluene solution 836.5g of 2 functionality phenylene ether oligomer bodies.2 functionality phenylene ether oligomer bodies Number-average molecular weight is 986, weight average molecular weight 1530, hydroxyl equivalent 471.

(synthesis of vinyl compound)

The first of 2 functionality phenylene ether oligomer bodies is put into the reactor for having agitating device, thermometer, return duct Benzole soln 836.5g, 1-chloro-4-methyl-benzene (trade name CMS-P, AGC SEIMI CHEMICAL CO., LTD. system) 162.6g, two Chloromethanes 1600g, benzyl dimethylamine 12.95g, pure water 420g, 30.5wt%NaOH aqueous solution 178.0g, in 40 DEG C of reaction temperature Under be stirred.After carrying out stirring in 24 hours, cleans organic layer with the aqueous hydrochloric acid solution of 1N, then cleaned with pure water.It will Acquired solution is concentrated with evaporator, is added dropwise into methanol and is carried out solid state, is recycled solid by filtering, is carried out vacuum It is dry, obtain vinyl compound 503.5g.The number-average molecular weight of vinyl compound is 1187, weight average molecular weight 1675, Vinyl equivalents are 590g/ vinyl.

(embodiment 1)

(making of resin combination and prepreg)

The methyl ethyl ketone of the silica-coating PTFE fillers of fluorinated resin particle (A) will be covered as silica (hereinafter, having When be abbreviated as MEK) slurry (0.5 μm of PTFE-YA (trade name), 0.5 μm of the volume average particle size of primary particle, nonvolatile component 20 mass %, Admatechs Company Limited systems) 250 mass parts (50 mass parts are calculated as with nonvolatile component conversion), As obtained in the synthesis example 1 of cyanate esters 2.1 mass parts of SNCN, 2,2- bis- (4- cyanatophenyls) propane Prepolymer (CA210 (trade name), cyanate equivalent 139, Mitsubishi Gas Chemical Co., Ltd's system) 6.6 mass parts, as epoxy Brominated bisphenol a type epoxy resin (E153 (trade name), epoxide equivalent 400, secondary hydroxyl amount 0.3meq/g, the DIC strain formula meeting of resin Society's system) 10.6 mass parts, as the vinyl compound obtained in the synthesis example 2 of the compound with ethylenically unsaturated group (number-average molecular weight 1187, vinyl equivalents are 590g/ vinyl) 77.5 mass parts, a-Methylstyrene Low-Polymer (KA3085 (trade name), matter average molecular weight：664, U.S. Eastman Chemical Company systems) 3.2 mass parts, conduct MEK slurries (SC2050MNU (trade name), the median particle diameter of the vinyl silanes processing silica of other packing materials (C) 0.5 μm, 70 mass %, Admatechs Company Limited systems of nonvolatile component) 71.4 mass parts are (with nonvolatile component Conversion is calculated as 50 mass parts) mixing, obtain varnish (solution of resin combination).The varnish methyl ethyl ketone is diluted and infiltrates painting The E glass woven fabrics of thickness 0.1mm are distributed in, 5 minutes heat dryings are carried out at 160 DEG C, obtain the pre- of 50 mass % of resin content Leaching material.

(making of internal layer circuit substrate)

With MEC COMPANY LTD. CZ8100 (trade name) to being formed with the internal layer electricity that minimum wiring spacing is 10 μm Glass cloth base material BT resins two sides copper-clad laminated board (12 μm of copper thickness, thickness 0.2mm, Mitsubishi's gas chemistry strain formula meeting on road Society CCL (registered trademark)-HL832NS (trade name)) two sides carry out the roughening treatment on copper surface, obtain internal layer circuit base Plate.

(making of metal-clad laminate)

Aforementioned prepreg is configured at internal layer circuit substrate or more, in the electrolytic copper foil (3EC-M3- of 12 μ m-thicks of configuration up and down VLP (trade name), Mitsui Metal Co., Ltd.'s Co. Ltd. system), in pressure 30kgf/cm², stacking in 120 minutes is carried out at 220 DEG C of temperature Thus molding obtains metal-clad laminate made of internal layer circuit substrate, resin composition layer and copper foil are laminated.

(making of evaluation solidfied material)

By 4 aforementioned prepreg overlappings and in electrolytic copper foil (3EC-M3-VLP (trade name), three of 12 μ m-thicks of configuration up and down Well metal Co. Ltd. system), in pressure 30kgf/cm², stacking molding in 120 minutes is carried out at 220 DEG C of temperature, obtain insulating layer The clad with metal foil plywood of thickness 0.4mm.The entire metal foil of gained clad with metal foil plywood is etched into removal, evaluation is obtained and uses Solidfied material.

(embodiment 2)

The volume average particle size of primary particle used as silica covering fluorinated resin particle (A) is the two of 3.0 μm The MEK slurries of silica coating PTFE fillers (PTFE-YA4 (trade name), 3.0 μm of the volume average particle size of primary particle, are not waved Hair ingredient 40 mass %, Admatechs Company Limited systems) 125 mass parts (are calculated as 50 matter with nonvolatile component conversion Measure part), it in addition to this, operates similarly with example 1, prepares varnish, obtain prepreg, metal-clad laminate, evaluation use Solidfied material.

(embodiment 3)

MEK slurries (0.5 μ of the silica-coating PTFE fillers of fluorinated resin particle (A) will be covered as silica MPTFE-YA (trade name), 0.5 μm of the volume average particle size of primary particle, 20 mass %, Admatechs of nonvolatile component Company Limited systems) 250 mass parts (50 mass parts are calculated as using nonvolatile component conversion), as cyanate esters Prepolymer (CA210 (the commodity of 2.0 mass parts of SNCN, bis- (4- cyanatophenyls) propane of 2,2- that are obtained in synthesis example 1 Name), cyanate equivalent 139, Mitsubishi Gas Chemical Co., Ltd's system) 6.2 mass parts, the bmminated bisphenol-A type as epoxy resin Epoxy resin (E153 (trade name), epoxide equivalent 400, secondary hydroxyl amount 0.3meq/g, Dainippon Ink Chemicals's system) 10.0 mass parts, As obtained in the synthesis example 2 of the compound with ethylenically unsaturated group vinyl compound (number-average molecular weight 1187, Vinyl equivalents be 590g/ vinyl) 72.8 mass parts, a-Methylstyrene Low-Polymer (KA3085 (trade name), the equal molecule of matter Amount：664, U.S. EastmanChemicalCompany systems) 3.0 mass parts, as the vinyl silanes of other packing materials (C) Handle silica MEK slurries (SC2050MNU (trade name), 0.5 μm of median particle diameter, 70 mass % of nonvolatile component, Admatechs Company Limited systems) 71.4 mass parts (50 mass parts are calculated as using nonvolatile component conversion), as fire-retardant Brominated polycarbonate (FG8500 (trade name), Teijin Ltd's system, 58 weight % of bromine content) 6 mass parts of agent (D) mix, Obtain varnish.It operates similarly with example 1 later, obtains prepreg, metal-clad laminate, evaluation solidfied material.

(embodiment 4)

(making of resin combination and resin sheet)

MEK slurries (0.5 μ of the silica-coating PTFE fillers of fluorinated resin particle (A) will be covered as silica MPTFE-YA (trade name), 0.5 μm of the volume average particle size of primary particle, 20 mass %, Admatechs of nonvolatile component Company Limited systems) 250 mass parts (50 mass parts are calculated as using nonvolatile component conversion), as cyanate esters Prepolymer (CA210 (the commodity of 2.1 mass parts of SNCN, bis- (4- cyanatophenyls) propane of 2,2- that are obtained in synthesis example 1 Name), cyanate equivalent 139, Mitsubishi Gas Chemical Co., Ltd's system) 6.6 mass parts, the bmminated bisphenol-A type as epoxy resin Epoxy resin (E153 (trade name), epoxide equivalent 400, secondary hydroxyl amount 0.3meq/g, Dainippon Ink Chemicals's system) 10.6 mass parts, As obtained in the synthesis example 2 of the compound with ethylenically unsaturated group vinyl compound (number-average molecular weight 1187, Vinyl equivalents be 590g/ vinyl) 77.5 mass parts, a-Methylstyrene Low-Polymer (KA3085 (trade name), the equal molecule of matter Amount：664, U.S. EastmanChemicalCompany systems) 3.2 mass parts, as the vinyl silanes of other packing materials (C) Handle silica MEK slurries (SC2050MNU (trade name), 0.5 μm of median particle diameter, 70 mass % of nonvolatile component, Admatechs Company Limited systems) 71.4 mass parts (50 mass parts are calculated as with nonvolatile component conversion) mixing, it obtains Varnish.These varnish are coated on to electrolytic copper foil (3EC-M2S-VLP (trade name), Co., Ltd. of Mitsui Metal Co., Ltd. of 12 μm of thickness System) on, 5 minutes heat dryings are carried out at 120 DEG C, obtain by the thickness of supporter and resin composition layer of copper foil being 40 μm Resin sheet.

(making of metal-clad laminate)

By aforementioned the internal layer circuit substrate used in embodiment 1 is configured by the resin face of the resin sheet of supporter of copper foil On, in pressure 30kgf/cm², stacking molding in 120 minutes is carried out at 220 DEG C of temperature, thus obtain internal layer circuit substrate, resin Metal-clad laminate made of composition layer and copper foil stacking.

(making of evaluation solidfied material)

The entire metal foil of gained metal-clad laminate is etched into removal, obtains evaluation solidfied material.

(comparative example 1)

Instead of silica covering fluorinated resin particle (A), PTFE dispersion liquids (EXP.FD-030 (trade name), intermediate value are used 0.5 μm of grain size, 40 mass % of nonvolatile component, Dainippon Ink Chemicals's system) 125 mass parts (with nonvolatile component conversion be calculated as 50 matter Measure part), it in addition to this, operates similarly to Example 3, prepares varnish, obtain prepreg, metal-clad laminate, evaluation use Solidfied material.

(comparative example 2)

Without using silica covering fluorinated resin particle (A), as other packing materials (C), at vinyl silanes Manage silica MEK slurries (SC2050MNU (trade name), 0.5 μm of median particle diameter, 70 mass % of nonvolatile component, Admatechs Company Limited systems) 142.9 mass parts (with nonvolatile component conversion be calculated as 100 mass parts), except this with Outside, it operates similarly with example 1, prepares varnish, obtain prepreg, metal-clad laminate, evaluation solidfied material.

(embodiment 5)

MEK slurries (0.5 μ of the silica-coating PTFE fillers of fluorinated resin particle (A) will be covered as silica MPTFE-YA (trade name), 0.5 μm of the volume average particle size of primary particle, 20 mass %, Admatechs of nonvolatile component Company Limited systems) 250 mass parts (50 mass parts are calculated as using nonvolatile component conversion), as maleimide chemical combination Maleimide compound (BMI-2300 (trade name), Daiwa Kasei Industry Co., Ltd.'s system) 3.5 mass parts of object, as ring Biphenyl aralkyl-type epoxy resin (NC3000H (trade name), Nippon Kayaku K. K's system) 19.8 mass parts of oxygen resin are made For the propylene glycol monomethyl ether second of the sour modified bisphenol F type rings oxypropylene ester compound of the compound with ethylenically unsaturated group Acid esters (hereinafter, be abbreviated as PMA sometimes.) solution (KAYARAD (registered trademark) ZFR-1553H (trade name), nonvolatile component 68 Quality %, acid value：70mgKOH/g, Nippon Kayaku K. K's system) 77.6 mass parts (with nonvolatile component conversion be calculated as 52.8 Mass parts), dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA (trade name), Nippon Kayaku K. K System) 18.9 mass parts, 2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls)-butanone-as trigger for optical solidification (E) 1 (Irgacure (registered trademark) 369 (trade name), BASF Japan Ltd. systems) 5 mass parts are compounded, and use ultrasonic homogenizer It is stirred, obtains varnish (solution of resin combination).These varnish are coated on to the PET film (Unipeel of 38 μm of thickness (registered trademark) TR1-38, Unitika Ltd. systems, trade name) on, 7 minutes heat dryings are carried out at 80 DEG C, are obtained with PET Film is the resin sheet that the thickness of supporter and resin composition layer is 40 μm.

(making of evaluation laminated body)

By aforementioned internal layer circuit used in embodiment 1 is configured at by the resin face of the resin sheet of supporter of PET film On substrate, using vacuum laminator (Nikko-Materials Co., Ltd.s system) vacuumize (5.0MPa or less) within 30 seconds Afterwards, in pressure 10kgf/cm², 30 seconds cascading into shape is carried out under temperature 70 C.And then in pressure 10kgf/cm², temperature 70 C It is lower to carry out 60 seconds cascading into shape, to obtain layer made of internal layer circuit substrate, resin composition layer and supporter stacking Stack.Irradiation 200mJ/cm is implemented to obtained laminated body²Ultraviolet light exposure process, remove supporter, with 1 mass %'s Aqueous sodium carbonate develops, and evaluation laminated body is made.

(making of evaluation solidfied material)

200mJ/cm is irradiated to aforementioned resin piece²Ultraviolet light, and then implement carry out 180 DEG C, 120 minutes heat treatment Then post-bake process removes supporter, evaluation solidfied material is made.

(embodiment 6)

MEK slurries (0.5 μ of the silica-coating PTFE fillers of fluorinated resin particle (A) will be covered as silica MPTFE-YA (trade name), 0.5 μm of the volume average particle size of primary particle, 20 mass %, Admatechs of nonvolatile component Company Limited systems) 100 mass parts (with nonvolatile component conversion be calculated as 20 mass parts), maleimide compound (BMI-2300 (trade name), Daiwa Kasei Industry Co., Ltd.'s system) 3.5 mass parts, the biphenyl aralkyl-type as epoxy resin Epoxy resin (KAYARAD (registered trademark) NC3000H (trade name), Nippon Kayaku K. K's system) 19.8 mass parts, conduct PMA solution (the KAYARAD of the sour modified bisphenol F type rings oxypropylene ester compound of compound with ethylenically unsaturated group (registered trademark) ZFR-1553H (trade name), 68 mass % of nonvolatile component, acid value：70mgKOH/g, Japanese chemical drug strain formula meeting Society's system) 77.6 mass parts (with nonvolatile component conversion be calculated as 52.8 mass parts), dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA (trade name), Nippon Kayaku K. K's system) 18.9 mass parts, as the ring of other packing materials (C) Oxosilane handles MEK slurries (SC2050MB (trade name), 0.5 μm of median particle diameter, 70 matter of nonvolatile component of silica Amount %, Admatechs Company Limited systems) 42.9 mass parts (with nonvolatile component conversion be calculated as 30 mass parts), make For 2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls)-butanone -1 (Irgacure (registrations of trigger for optical solidification (E) Trade mark) 369 (trade names), BASF Japan Ltd. systems) compounding of 5 mass parts, be stirred, obtained clear with ultrasonic homogenizer Paint.It operates similarly to Example 5 later, obtains resin sheet, evaluation laminated body, evaluation solidfied material.

(embodiment 7)

As silica covering fluorinated resin particle (A), the dioxy that the volume average particle size using primary particle is 3.0 μm The MEK slurries that SiClx is coated with PTFE fillers are (PTFE-YA4 (trade name), 3.0 μm of the volume average particle size of primary particle, non-volatile 40 mass %, Admatechs Company Limited systems of ingredient) 125 mass parts (with nonvolatile component conversion be calculated as 50 mass Part), it in addition to this, operates similarly to Example 5, prepares varnish, obtain resin sheet, evaluation laminated body, evaluation solidification Object.

(embodiment 8)

As the compound with ethylenically unsaturated group, instead of sour modified bisphenol F type rings oxypropylene ester compound PMA solution (KAYARAD (registered trademark) ZFR-1553H (trade name), 68 mass % of nonvolatile component, acid value：70mgKOH/g、 Nippon Kayaku K. K's system), use the PMA solution of TrisP-PA epoxy acrylic ester compounds shown in formula (4) (KAYARAD (registered trademark) ZCR-6007H (trade name), 65 mass % of nonvolatile component, acid value：70mgKOH/g, Japanization Medicine Co. Ltd. system) 81.2 mass parts (52.8 mass parts are calculated as with nonvolatile component conversion), it is in addition to this, same with embodiment 5 It operates to sample, prepares varnish, obtain resin sheet, evaluation laminated body, evaluation solidfied material.

It should be noted that aforementioned KAYARAD (registered trademark) ZCR-6007H is comprising above compound (A1) and above-mentioned The mixture of any one of compound (A2)~(A5) or more.

(comparative example 3)

Instead of silica covering fluorinated resin particle (A), PTFE dispersion liquids (EXP.FD-030 (trade name), intermediate value are used 0.5 μm of grain size, 40 mass % of nonvolatile component, Dainippon Ink Chemicals's system) 125 mass parts (with nonvolatile component conversion be calculated as 50 matter Measure part), it in addition to this, operates similarly to Example 5, prepares varnish, obtain resin sheet, evaluation laminated body, evaluation with admittedly Compound.

(comparative example 4)

It is handled using epoxy silane as other packing materials (C) without using silica covering fluorinated resin particle (A) MEK slurries (SC2050MB (trade name), 0.5 μm of median particle diameter, 70 mass %, Admatechs of nonvolatile component of silica Company Limited systems) 71.4 mass parts (50 mass parts are calculated as with nonvolatile component conversion), in addition to this, with embodiment 5 It similarly operates, prepares varnish, obtain resin sheet, evaluation laminated body, evaluation solidfied material.

(physical property measurement evaluation)

Metal-clad laminate, evaluation laminated body and evaluation are measured with solidfied material by the following method, commented Valence.By it is shown in table 1 in their result set~3.

For the entire copper foil of more than half etching of the single side of the sample of metal-clad laminate 50mm × 50mm is gone The test film of test film obtained from removing or evaluation laminated body 50mm × 50mm, with pressure cooker testing machine, (Pingshan Mountain makes institute's strain Formula commercial firm system, PC-3 types), carry out under 121 DEG C, 2 air pressures processing in 5 hours after, impregnate 60 seconds in 260 DEG C of solder, so The visually variation of observation appearance afterwards, is evaluated according to benchmark below.

◎：In 5 test films, does not observe and heave.

○：In 5 test films, observes for 1 and heave.

×：In 5 test films, observes for 2 or more and heave.

The test film of the test film or evaluation laminated body 50mm × 50mm that make metal-clad laminate 50mm × 50mm exists It is floated 30 minutes in 280 DEG C of solders, visually whether there is or not abnormal appearances for observation, are evaluated according to benchmark below.

○：In 5 test films, does not observe and heave.

×：In 5 test films, observes for 1 or more and heave.

With cavity resonator perturbation method (Agilent (registered trademark) 8722ES, Agilent Technologies, Inc. System) dielectric constant and dielectric loss angle tangent of 10GHz are measured to the test film of evaluation solidfied material.

Visually behind the development face of observation evaluation laminated body, (1000 times of multiplying power) is observed with SEM, according to following benchmark Evaluate the presence or absence of residue.

○：There is no development residue, developability excellent in the range of 30mm square.

×：There are development residue, developability poor in the range of 30mm square.

To evaluation solidfied material, DMA device (TA INSTRUMENTS corporation measurement of dynamic viscoelasticity device is used DMAQ800 (trade name)), it is heated up with 10 DEG C/min, using the peak position of loss modulus (LossModulus) as glass Change transition temperature (Tg).

[table 1]

Project

Embodiment 1

Embodiment 2

Embodiment 3

Embodiment 4

Comparative example 1

Comparative example 2

Connect up embeddability

◎

○

◎

×

◎

Solder heat resistance

○

×

○

Dielectric constant (10GHz)

3.1

3.2

2.6

3.2

3.3

Dielectric loss angle tangent (10GHz)

0.003

[table 2]

Project	Embodiment 5	Embodiment 6	Embodiment 7	Comparative example 3	Comparative example 4
						Connect up embeddability	◎	◎	○	×	◎
Solder heat resistance	○	○	○	×	○
						Dielectric constant (10GHz)	2.7	2.8	2.7	2.7	2.9
Dielectric loss angle tangent (10GHz)	0.016	0.016	0.016	0.016	0.016
						Developability	○	○	○	○	○

[table 3]

Project	Embodiment 8	Embodiment 5
			Connect up embeddability	◎	◎
Solder heat resistance	○	○
			Dielectric constant (10GHz)	2.7	2.7
Dielectric loss angle tangent (10GHz)	0.016	0.016
			Developability	○	○
Heat resistance (Tg (DEG C))	162	133

It can be defined according to table 1, table 2 and table 3, the wiring embeddability and excellent heat resistance of Examples 1 to 8, dielectric constant, Dielectric loss angle tangent is good.Wherein, the wiring embeddability of embodiment 1, embodiment 4 and embodiment 5, dielectric constant are good.It is real Apply example 8 and then heat resistance (Tg) it is high, be good.In contrast, wiring embeddability, heat resistance and the dielectric constant of comparative example 1~4 Any one of it is insufficient.Therefore, according to the present invention, dielectric constant, dielectric loss angle tangent, fine wiring insertion can be obtained Property, the excellent resin combination of heat resistance, developability, use its prepreg, clad with metal foil plywood, resin sheet, printing electricity Road plate and semiconductor device.

Claims

1. a kind of resin combination contains silica covering fluorinated resin particle (A) and resin component (B).

2. resin combination according to claim 1, wherein the silica covers the primary of fluorinated resin particle (A) The volume average particle size of particle is 5 μm or less.

3. resin combination according to claim 1 or 2, wherein the silica covering fluorinated resin particle (A) is being set Content in oil/fat composition is 3~400 mass parts relative to 100 mass parts of resin solid content in resin combination.

4. resin combination described in any one of claim 1 to 3, wherein the resin component (B) contain selected from by Maleimide compound, cyanate esters, epoxy resin, phenolic resin, oxetane resin, benzoxazine compound And more than any one of group of compound composition with ethylenically unsaturated group.

5. resin combination according to any one of claims 1 to 4, wherein also contain except the silica covers Packing material (C) other than fluorinated resin particle (A).

6. resin combination according to any one of claims 1 to 5, wherein also contain fire retardant (D).

7. according to resin combination according to any one of claims 1 to 6, wherein also contain trigger for optical solidification (E).

8. resin combination according to claim 4, wherein the compound with ethylenically unsaturated group includes choosing Freely there is at least one in the group of 2 functionality phenylene ether oligomers of vinyl and the oligomer composition of α-methylstyrene Kind or more.

9. resin combination according to claim 4, wherein the compound with ethylenically unsaturated group includes choosing Free acid modified bisphenol F type rings oxygen (methyl) acrylate, six (first of the following general formula (1) compound represented and dipentaerythritol Base) acrylate composition at least one of group more than,

In formula (1), multiple R₁Each independently represent hydrogen atom or methyl, multiple R₂Hydrogen atom or methyl are each independently represented, Multiple R₃Substituent group or hydroxyl shown in substituent group, following formula (3) shown in following formula (2) are each independently represented,

In formula (3), R₄Indicate hydrogen atom or methyl.

10. resin combination according to claim 9, wherein the compound with ethylenically unsaturated group is at least Including general formula (1) compound represented.

11. a kind of prepreg with base material and infiltration or is coated on the according to any one of claims 1 to 10 of the base material Resin combination.

12. a kind of clad with metal foil plywood has the prepreg described in the claim 11 of stacking at least 1 or more and configuration In the metal foil of the one or two sides of the prepreg.

13. a kind of resin sheet, with any one of supporter and the claim 1~10 on surface for being configured at the supporter institute The resin combination stated.

14. a kind of printed circuit board, with resin combination according to any one of claims 1 to 10.

15. a kind of semiconductor device, with resin combination according to any one of claims 1 to 10.