CN110520475A - Hardening resin composition, dry film, solidfied material, electronic component and printed circuit board - Google Patents

Abstract

There is provided can obtain being able to maintain that the hardening resin composition of the excellent solidfied material of the various characteristics such as low thermal expansion rate and toughness, using its dry film, solidfied material and electronic component the high-temperature area in component installation.A kind of hardening resin composition, it includes: the filler other than curable resin, at least one-dimensional fine powder and fine powder less than 100nm.Use the dry film, solidfied material and electronic component of the hardening resin composition.

Description

Hardening resin composition, dry film, solidfied material, electronic component and printed circuit board

Technical field

The present invention relates to hardening resin composition, dry film, solidfied material and electronic components.Moreover, it relates to solidify Property resin combination, solidfied material and printed circuit board.

Background technique

As electronic component, there are wiring plate, the active parts for being fixed on wiring plate, passive component etc..In wiring plate, have pair Insulating substrate apply electric conductor wiring and by persons of being connected and fixed such as active parts, passive components, depending on the application, sometimes will be exhausted Edge layer and conductor layer carry out multiple stratification or use flexible insulating substrate, become important electronics in the electronic device Component.In addition, wiring plate is also used in semiconductor packages, wiring plate hardening resin composition, dry film are as wiring plate Or semiconductor installation after outer layer come using.As active parts, passive component, can enumerate transistor, diode, resistance, Coil, capacitor etc..

In recent years, with the miniaturization of electronic equipment, the requirement characteristic to electronic component becomes stringent.About wiring plate, The densification of wiring is gradually required, in order to ensure wiring, the reliability of component interconnecting piece, the material of wiring plate is gradually required Lower thermal expansivity.Active parts, passive component also require miniaturization, highly integrated, similarly in order to ensure reliability, by Gradually require lower thermal expansivity.

As the method for reaching low heat expansion, such as propose makes Inorganic Fillers Filled in resin in patent document 1 And the method for obtaining low thermal expansion rate.

In addition, the means as the low heat expansion for reaching this material, such as propose and carried out by force with cellulose fibre Change and be made the method for fibre reinforced composites (referring to patent document 2).

In turn, in recent years, with the miniaturization of electronic equipment, in order to efficiently transmit high-frequency, to electronic component requirement Low dielectric property.There is bicyclopentadiene as proposing to use in the method for reaching low dielectric property, such as non-patent literature 1 The epoxy resin of skeleton is come the method that reduces relative dielectric constant and dielectric loss angle tangent.

In turn, in recent years, with the high performance of electronic equipment, it is desirable that the more higher frequency than in the past wants electronic component It asks and efficiently transmits high-frequency.As high-frequency characteristic, kelvin effect can be enumerated.Such as it is illustrated in non-patent literature 2 As frequency increases, electric current become can only be by the surface of conductor near.

In addition, in recent years, in order to cope with the miniaturization multifunction for the equipment for having printed circuit board, printed circuit board More light and shortization be in progress.Therefore, the conductor circuit of printed circuit board requires further graph thinning and mounting area Downsizing.

In contrast, in the manufacturing method of printed circuit board, widely with the following method: being set to leading for wiring plate Potting resin filler and make its solidification in the recess portions such as through-hole, through-hole or through hole, carries out after grinding forms even surface, described Insulating layer and conductor laminated layer are further carried out to the technical side of multiple stratification on via hole, through-hole filled with resin filler Method.

As resin filler used in this technical method, it is desirable that the fillibility of recess portion, through hole, solidfied material The material of each excellent such as abrasiveness, heat resistance, proposes hot curing resin composition as patent document 3.

On the other hand, by it is higher it is densification for the purpose of, recently using in the conducting filled with resin filler The wiring of conductor pad, via hole etc. is set on the recess portions such as hole, through-hole or through hole to carry out the technical method of component installation.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2001-72834 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2011-001559 bulletin

Patent document 3: Japanese Unexamined Patent Publication 2015-10146 bulletin

Non-patent literature

Non-patent literature 1: " Journal of network polymer " Vol.17, No.2 (1996) pp69

Non-patent literature 2: No. 1 page (2013) 18~20 of volume 61 of " Physical Education "

Summary of the invention

Problems to be solved by the invention

However, in material described in patent document 1, desired low thermal expansion rate in order to obtain, it is necessary to which filling is a large amount of Inorganic filler, the problem of the physical property difference of the solidfied materials such as flexible.

In turn, the inventors discovered that, for the material recorded in patent document 1, more than 200 DEG C as component installation when Temperature region have biggish coefficient of thermal expansion, can generate in order to ensure the ineffective new problem of reliability.

Therefore, the first object of the present invention is to provide a kind of hardening resin composition, can obtain even if in portion High-temperature area when part is installed such as can also maintain low thermal expansion rate and can obtain toughness at the solidfied material of each excellent.

Of the invention first it is other be designed to provide using the dry film of above-mentioned hardening resin composition, solidfied material and Electronic component.

In addition, really, according to the material recorded in patent document 2, making the fiber point of 4~200nm of avarage fiber diameter It is dispersed in host material, therefore the composite material of low heat expansion can be obtained.

However, in order to further increase low heat expansion, cellulose fibre is selected in the method described in Patent Document 2, On the other hand, inventors noted that for miniaturization, densification, highly integrated purpose and prepare the electronics of stepped construction In the case where component, it is new in this way especially to there is a problem of that the insulating reliability of interlayer deteriorates.

Therefore, the second object of the present invention is to provide a kind of hardening resin composition, is low heat expansion, and Even if for miniaturization, densification, highly integrated purpose and in the case where the electronic component of stepped construction is made, also can Obtain the excellent solidfied material of the insulating reliability of interlayer.

The other purpose of of the invention second is, provides dry film, the solidfied material using above-mentioned hardening resin composition And electronic component.

In turn, in the high-frequency of electronic component, not only have low dielectric property, but also be capable of forming the circuit of fine Also quite important.The point, although the insulating layer that non-patent literature 1 is recorded can obtain low dielectric property, the inventors discovered that It is unable to get the dhering strength with the circuit of fine (copper facing).

Therefore, the third object of the present invention is to provide a kind of hardening resin composition, can obtain having low Jie Electrical characteristics and solidfied material and the good solidfied material of copper-plated adaptation.

In addition, in addition third of the invention is designed to provide the dry film using above-mentioned hardening resin composition, solidification Object and electronic component.

In turn, above-mentioned kelvin effect refers to can show in the wiring in electronic component, high-frequency can only pass through cloth The extreme surface of line.Therefore, in order to efficiently transmit high-frequency, consider the interface of the wiring of electronic component and insulating materials Smoothing.

But if carrying out this smoothing, there are insulating materials and the copper-plated adaptation for constituting wiring (to remove strong Degree) reduce the problem of.

On the other hand, it is improved to make to constitute the copper-plated adaptation being routed, bottom when insulating materials being drilled with laser While removing (de-smear) of the glue residue of generation, usually carry out insulating materials surface roughening.

However, if carrying out this roughening, can lead to the problem of can not efficiently transmit it is high-frequency.

Therefore, the 4th main purpose of the invention is to provide a kind of hardening resin composition, can be in de-smear The glue residue generated by laser processing is removed in process, while can also obtain having transmitting advantageous small rough surface to high-frequency Degree and peel strength also excellent solidfied material.

In addition, in addition the of the invention the 4th is designed to provide the dry film using above-mentioned hardening resin composition, solidification Object and electronic component.

In turn, really, according to the material recorded in patent document 2, make the fiber point of 4~200nm of avarage fiber diameter It dissipates in host material, therefore the composite material of low heat expansion can be obtained.

However, the inventors discovered that, for above-mentioned composite material, if copper facing is formed solid shape on material, can produce It is new in this way that the raw copper facing due to thermal history of component installation etc. leads to the problem of expansion.

Therefore, the 5th main purpose of the invention is to provide a kind of hardening resin composition, can obtain being low Thermal expansivity, and even if apply copper plating, for in addition to cloth for the purpose for manufacturing wiring on the solidfied material of composition Except line pattern carry out electromagnetic wave shielding purpose and by copper facing formed solid shape in the case where, copper facing will not be produced because of thermal history Raw expansion, thermo-tolerance also excellent solidfied material.

In addition of the invention the 5th is designed to provide dry film, solidfied material and electricity using above-mentioned hardening resin composition Subassembly.

In turn, for the material recorded in patent document 1, desired low thermal expansion rate in order to obtain, it is necessary to a large amount of fillings There is the physical property difference of the solidfied materials such as toughness in inorganic filler.

In turn, the present inventors find, about the material recorded in patent document 1, more than 200 DEG C as component installation When temperature region in will form biggish coefficient of thermal expansion, in order to ensure reliability, there is a problem of that no effect is new in this way.

Therefore, the sixth object of the present invention is to provide a kind of hardening resin composition, can obtain even if in portion High-temperature area when part is installed can also maintain the solidfied material of each excellent such as lower coefficient of thermal expansion and toughness, heat resistance.

In addition of the invention the 6th is designed to provide dry film, solidfied material and electricity using above-mentioned hardening resin composition Subassembly.

In turn, above-mentioned technical method used in the manufacturing method for printed circuit board, if such using patent document 3 Hot curing resin composition as resin filler, then there are the following problems: being led with what resin filler was filled High-temperature heating work of the metal line of conductor pad, via hole on the recess portions such as through-hole, through-hole, through hole etc. when component is installed It can be expanded in sequence, this expansion can impact reliability.

In addition, being filled in the hot curing resin composition of recess portion, through hole (hereinafter also referred to as " hole portion etc. "), resin Ingredient melts and solidifies because of heating, therefore there are problems that ooze out on peripheries such as hole portions when solidification.Due to this exudation The filler ingredient of resin combination is thin, so because that its adhesiveness can not completely remove in the grinding of next process is residual The reason of staying, becoming the unfavorable condition of plating.

In turn, be filled in recess portion, through hole hot curing resin composition solidification after grinding process in, it is also desirable to The exudation of the resin filler on the peripheries such as hole portion is completely removed, as a result, also having can generate in hole portion etc. because of excessive grinding Recess, the other problems that complete even surface can not be become.

Therefore, the 7th main purpose of the invention is to provide the hardening resin composition for being able to solve the above subject, Following hardening resin composition is specifically provided: though component installation when high-temperature heating process in, filled with resin The wiring of conductor pad, via hole on the recess portions such as via hole, through-hole that agent is filled, through hole etc. will not generate swollen It is swollen, it there will not be the exudation of the thin resin combination of filler ingredient when moreover, solidifying, in the grinding process after solidification also not Can generate in order to smooth and overmastication caused by hole portion etc. recess.

7th other purposes of the invention are to provide the solidification for the hardening resin composition for being able to solve the above subject Object and the printed circuit board of hole portion etc. is filled with the solidfied material.

The solution to the problem

The present inventors has made intensive studies, as a result, it has been found that, relative in the past as solder resist, interlayer dielectic, The packing material of the electronic part materials such as filling perforation material and silica, calcium carbonate, barium sulfate, talcum, the titanium oxide etc. used Filler is compounded by the way that at least one-dimensional fine powder (hereinafter also referred to as " fine powder ") less than 100nm is applied in combination, from And it is unexpectedly able to solve the above problem, solve the present invention.

That is, the hardening resin composition of first embodiment of the invention, characterized by comprising: curable resin, Filler other than at least one-dimensional fine powder and the fine powder less than 100nm.

In the present invention, it is appropriate that, as aforementioned fine powder, (hereinafter also referred to as using fine cellulose powder " CNF ") or Cellulose nanocrystal particle (hereinafter also referred to as " CNC ").In addition, other than aforementioned fine powder and the fine powder Mix ratio of the filler in total filler be suitably for (filler other than fine powder: fine powder)=100 by quality ratio: (0.04~30).

Present invention it is preferred that said curing property resin includes at least wantonly a kind of the ring with naphthalene skeleton and anthracene skeleton Shape ether compound or comprising selected from by the cyclic ether compound with bicyclopentadiene skeleton and with bicyclopentadiene skeleton At least one kind of in the group of phenolic resin composition or comprising phenoxy resin or comprising selected from by the cyclic ether with biphenyl backbone It is at least one kind of in the group of compound and the phenolic resin composition with biphenyl backbone.

Dry film of the invention, which is characterized in that have and above-mentioned hardening resin composition is coated on film and is dried Made of resin layer.

Solidfied material of the invention, which is characterized in that it is by the aforementioned of above-mentioned hardening resin composition or above-mentioned dry film Made of resin layer solidification.

Electronic component of the invention, which is characterized in that have above-mentioned solidfied material.

Herein, in the present invention, Cellulose nanocrystal particle refer to by cellulosic material with the inorganic acid of high concentration (hydrochloric acid, Sulfuric acid, hydrobromic acid etc.) it hydrolyzes and removes non-crystallized part, only by crystalline portion segregator.Specifically, being with 7wt% or more Strong acid, the preferred easy strong acid of the strong acid of 9wt% or more, further preferred sulfuric acid etc high concentration and with 60wt% or more Concentration apply hydrolysis obtained from be free of non-crystallized part crystalline solid.

In addition, the present inventors has made intensive studies in face of solving the above subject, as a result, it has been found that, as printed circuit board The recess portions such as via hole, through-hole, through hole packing material, by using make at least one-dimensional fine powder less than 100nm and The hardening resin composition of Thermocurable ingredient dispersion completes the present invention to can solve the above subject.

The hardening resin composition of second embodiment of the present invention is characterized in that, for for being filled in printing electricity The recess portion of road plate and the hardening resin composition of at least one of through hole, it is at least one-dimensional micro- less than 100nm comprising (A) Fine powder and (B) Thermocurable ingredient.

It is the cyclic ether compound of precursor as (B) thermosetting that hardening resin composition of the invention, which is preferably comprised using amine, The property changed ingredient, additionally, it is preferred that including bisphenol A type epoxy resin and bisphenol f type epoxy resin.

Hardening resin composition of the invention preferably comprises (C) boric acid ester compound.

Solidification compound of the invention preferably comprises (D) filler other than above-mentioned (A) fine powder.

Solidfied material of the invention, which is characterized in that it is will be made of the solidification of said curing property resin combination.

Printed circuit board of the invention, which is characterized in that at least one of the recess portion of printed circuit board and through hole are preceding State hardening resin composition filling.

Herein, in the present invention, as fine powder, shape is not particularly limited, and threadiness, flakey, grain can be used The shapes such as shape, " at least one-dimensional to be less than 100nm " refer to that one-dimensional, two-dimentional and any one three-dimensional is less than 100nm.For example, fibrous Fine powder in the case where, can enumerate two dimension be less than 100nm and have to remaining one-dimensional extension person, it is squamaceous In the case where fine powder, it can be enumerated and be less than 100nm on one side, have to remaining two-dimensional extension person, granular is fine In the case where powder, three-dimensional respectively less than 100nm person can be enumerated.

In addition, one-dimensional, the two-dimentional and three-dimensional size in fine powder can use SEM (Scanning in the present invention Electron Microscope；Scanning electron microscope), TEM (Transmission Electron Microscope；Thoroughly Emitting electron microscope), AFM (Atomic Force Microscope；Atomic force microscope) etc. observation fine powder and survey It is fixed.

For example, squamaceous fine powder when, measure the average value of the smallest one-dimensional thickness, which set For less than 100nm.Specifically, the diagonal line in microscope photo is crossed, in its vicinity and the fine powder of thickness can be measured Body extracts out at 12 points at random, and after most thick fine powder and most thin fine powder removal, remaining 10 points of the thickness of measurement is set as Average value ratio 100nm is small.

For threadiness fine powder when, the average value for measuring the smallest two-dimensional fibre diameter is (hereinafter also referred to as " flat Equal fibre diameter "), which is set as smaller than 100nm.Specifically, the diagonal line in microscope photo is crossed, Fine powder positioned adjacent extracts out at 12 points at random, and the fine powder of most thick fibre diameter and most thin fibre diameter is gone After removing, it is small to be set as average value ratio 100nm for remaining 10 points of the fibre diameter of measurement.

When for granular fine powder, the average value of partial size is measured, which is set as to be less than 100nm.It is specific and Speech is crossed in the diagonal line of microscope photo, and fine powder positioned adjacent extracts out at 12 points at random, by maximum particle diameter and minimum After the fine powder removal of partial size, remaining 10 points of the partial size of measurement is set as average value less than 100nm.

There is the fine powder that extend to other dimensions for threadiness, flakey etc., extend be, for example, less than 1000nm, Preferably smaller than 650nm, it is further preferably no larger than 450nm.If extension is less than 1000nm, fine powder can be effectively obtained each other Interaction bring reinforcing effect.

It is same as above-mentioned fine powder about the definition of fine cellulose powder in the present invention.

The effect of invention

First, according to the present invention it is possible to provide a kind of hardening resin composition, can obtain installing even if in component When high-temperature area can also maintain the solidfied material of each excellent such as low thermal expansion rate and toughness.

In addition, according to the present invention it is possible to providing dry film, solidfied material and the ministry of electronics industry using above-mentioned hardening resin composition Part.

Second, according to the present invention it is possible to provide a kind of hardening resin composition, can obtain for low heat expansion, And when being made the electronic component of stepped construction for miniaturization, densification, highly integrated purpose, the insulating reliability of interlayer Also excellent solidfied material.

In addition, according to the present invention it is possible to providing dry film, solidfied material and the ministry of electronics industry using above-mentioned hardening resin composition Part.

Third can obtain having low dielectric special according to the present invention it is possible to provide a kind of hardening resin composition Property and solidfied material and the good solidfied material of copper-plated adaptation.

In addition, according to the present invention it is possible to providing dry film, solidfied material and the ministry of electronics industry using above-mentioned hardening resin composition Part.

4th, according to the present invention it is possible to provide a kind of hardening resin composition, can be removed in de-smear process Because of the glue residue that laser processing generates, while it can obtain having and advantageous small surface roughness is transmitted to high-frequency and is removed strong Spend also excellent solidfied material.

In addition, according to the present invention it is possible to providing dry film, solidfied material and the ministry of electronics industry using above-mentioned hardening resin composition Part.

5th, according to the present invention it is possible to provide a kind of hardening resin composition, can obtain as low heat expansion, And even if apply copper plating, for other than wiring pattern for the purpose for manufacturing wiring on the solidfied material of composition The purpose of electromagnetic wave shielding is carried out by the case where copper facing formation solid shape, copper facing will not generate expansion, height because of thermal history Warm patience also excellent solidfied material.

In addition, according to the present invention it is possible to providing the dry film, solidfied material and the ministry of electronics industry using the hardening resin composition Part.

6th, according to the present invention it is possible to provide a kind of hardening resin composition, can obtain installing even if in component When high-temperature area can also maintain the solidfied material of each excellent such as low thermal expansion rate and toughness, heat resistance, and working life is excellent It is different.

In addition, according to the present invention it is possible to providing dry film, solidfied material and the ministry of electronics industry using above-mentioned hardening resin composition Part.

7th, according to the present invention it is possible to provide a kind of hardening resin composition, with recess portion and through hole at least In the printed circuit board of one, though component installation when high-temperature heating process in, carried out filling with resin filler The wiring of conductor pad, via hole on the recess portions such as via hole, through-hole, through hole etc. will not generate expansion, moreover, when solidification It there will not be the exudation of the thin resin combination of filler ingredient, will not generate in the grinding process after solidification in order to smooth Change and excessive grinding caused by hole portion etc. recess.

In addition, according to the present invention it is possible to provide be able to solve the hardening resin composition of the above subject solidfied material, with And the printed circuit board of hole portion etc. is filled with the solidfied material.

Detailed description of the invention

Fig. 1-1 is the chart for indicating the relationship of compounding amount and coefficient of thermal expansion of silica and fine cellulose powder.

Fig. 1-2-1 is to indicate by the figure of the effect that the reduction of bring coefficient of thermal expansion is applied in combination of fine cellulose powder Table.

Fig. 1-2-2 is to indicate by the figure of the effect that the reduction of bring coefficient of thermal expansion is applied in combination of fine cellulose powder Table.

Fig. 1-3 is the chart that bring elongation improvement effect is applied in combination indicated by fine cellulose powder.

Fig. 1-4 is the explanatory diagram for indicating to test substrate used in embodiment.

Fig. 2-1 is the partial cross section for indicating a configuration example of the multilayer board of an example for electronic component of the invention Figure.

Fig. 2-2 is the explanatory diagram for indicating to test substrate used in embodiment.

Fig. 2-3 is other explanatory diagrams for indicating to test substrate used in embodiment.

Fig. 2-4 is another explanatory diagram for indicating to test substrate used in embodiment.

Fig. 3-1 is the partial cross section for indicating a configuration example of the multilayer board of an example for electronic component of the invention Figure.

Fig. 3-2 is the explanatory diagram for indicating to test substrate used in embodiment.

Fig. 4-1 is the partial cross section for indicating a configuration example of the multilayer board of an example for electronic component of the invention Figure.

Fig. 4-2 is the explanatory diagram for indicating to test substrate used in embodiment.

Fig. 5-1 is the partial cross section for indicating a configuration example of the multilayer board of an example for electronic component of the invention Figure.

Fig. 5-2 is the explanatory diagram for indicating to test substrate used in embodiment.

Fig. 6-1 indicates the chart of the relationship of the compounding amount and coefficient of thermal expansion of silica and Cellulose nanocrystal particle.

Fig. 6-2-1 is the figure that bring coefficient of thermal expansion reducing effect is applied in combination indicated by Cellulose nanocrystal particle Table.

Fig. 6-2-2 is the figure that bring coefficient of thermal expansion reducing effect is applied in combination indicated by Cellulose nanocrystal particle Table.

Fig. 6-3 is the chart that bring elongation improvement is applied in combination indicated by Cellulose nanocrystal particle.

Fig. 6-4 is the explanatory diagram for indicating to test substrate used in embodiment.

Fig. 7-1 is an example for indicating the manufacturing method of the printed circuit board using hardening resin composition of the invention Perspective cross-sectional slice.

Fig. 7-2 is to indicate that the part of a configuration example of the multilayer board of an example for printed circuit board of the invention is cut Face figure.

Fig. 7-3 is to indicate that the part of a configuration example of the multilayer board of an example for printed circuit board of the invention is cut Face figure.

Fig. 7-4 is the perspective cross-sectional slice being illustrated for the recess of the hole portion generated in grinding process etc..

Specific embodiment

Hereinafter, being described in detail for embodiments of the present invention.

<<first embodiment of the invention>>

The hardening resin composition of first embodiment of the invention, it is maximum to be characterized in that, it is applied in combination fine Filler other than powder and fine powder is as packing material this point.

By being set as such composition, about the first purpose, it can provide and be installed even if the component as more than 200 DEG C When temperature region can also maintain the solidfied material of each excellent such as low thermal expansion rate and toughness.

[fine powder]

Fine powder used in the present invention refers to that at least one-dimensional powder less than 100nm not only includes as described above Fine connects torulose powder, and includes the powder of threadiness of the diameter of section less than 100nm, thickness less than 100nm Sheet (flakey) powder etc..Any one of this fine powder and three-dimensional for the situation of 100nm or more compared with, often The surface area of unit mass can become much larger, increase in the ratio for the atom that surface is exposed.It is therefore contemplated that fine powder can be obtained Interaction that body is attracted each other and show reinforcing effect, thermal expansivity reduces.

It, can be with as long as at least one-dimensional particle smaller than 100nm, material are not particularly limited as fine powder Two or more is applied in combination.As fine powder, for example, graphite, graphene, fullerene, single-layer carbon nano-tube, multilayer The inorganic system such as the carbon such as carbon nanotube system, silver, gold, iron, nickel, titanium oxide, cerium oxide, zinc oxide, silica, aluminium hydroxide glues Fine cellulose powder obtained by the mineral such as soil, smectite, bentonite system and fiber detaching by plant and only by crystallization unit Point from the Cellulose nanocrystal particle that cellulosic material separates, by fine first obtained by the chitin fibrillation obtained as shell-fish etc. Shell element, to macromolecular of fine chitosan obtained by these fine chitin further progress alkali process etc. etc., can be by it Be processed into nanotube, nano wire, nano-sheet, two or more can also be applied in combination.Among these, as hydrophilic micro- Fine powder can enumerate the mineral systems such as the metal hydroxides such as the metal oxide microparticles such as titanium oxide, aluminium hydroxide particle, clay Particle, fine cellulose fiber, fine chitin etc..In this fine powder, especially it is easy from reinforcing effect and operation From the perspective of property, in addition, from the viewpoint of with the easiness of copper-plated adaptation improvement and operation, it is generally desirable to micro- Fine cellulose powder.In addition, it is also preferred that Cellulose nanocrystal particle.

As at least one-dimensional powder less than 100nm, inventors are conceived to fine cellulose powder, by its compounding amount with The relationship of coefficient of thermal expansion is compared and furthers investigate with silica, as a result, it has been found that, it, can be with using fine cellulose powder A small amount of compounding amount obtains the reducing effect (referring to Fig.1-1) of significant coefficient of thermal expansion.

In turn, inventors are conceived to the compounding using fine cellulose powder, can be obtained sufficiently with a small amount of compounding The reducing effect this point of coefficient of thermal expansion have made intensive studies, as a result, it has been found that, by being compounded for ensuring the electronics such as toughness The fillers such as silica of each characteristic required by the insulating materials of component, and the fine cellulose powder is applied in combination, from And the distinctive effect of aforementioned present invention (- 2,1-3 referring to Fig.1) can be obtained.

When using hydrophilic fine powder as fine powder as described above, preferably its particle is dredged Hydration process or the surface treatment etc. for implementing to use coupling agent.This processing, which can be used, is suitable for the known used of fine powder Method.

The compounding amount of fine powder in the present invention relative to the total amount for the composition for eliminating solvent be preferably 0.04~ 64 mass %, more preferably 0.08~30 mass %, further preferably 0.1~10 mass %.The compounding amount of fine powder is When 0.04 mass % or more, the reducing effect of linear expansion coefficient can be obtained well, in addition, can obtain well and copper facing Adaptation improvement.On the other hand, in 64 mass % situations below, film formation property is improved.

In fine powder of the invention, fine cellulose powder can obtain as follows, but be not limited to these.

(fine cellulose powder)

As the raw material of fine cellulose powder, can be used by timber, fiber crops, bamboo, cotton, jute, mestha, beet, agriculture Regenerated celulose fibres such as paper pulp, artificial silk, the glassine paper that the natural plant fibres raw material such as product waste, cloth obtains etc., In, particularly preferred paper pulp.As paper pulp, can be used by by plant material chemically or mechanicalness or to be applied in combination two Person come carry out it is pulped obtained from the chemical pulps such as kraft pulp, sulfite cellulose, semichemical wood pulp, chemical grinding paper pulp, Chemimechanical pulp, thermomechanical pulp, chemical thermo-mechanical pulp, refiner mechanical pulps, photogrammetry pulp mill and by these plant fibers Deinked waste paper paper pulp, waste magazine paper paper pulp, secondary corrugating material paper pulp etc. as principal component.Wherein, the strong source of the intensity of fiber From the various kraft pulps of coniferous tree, the non-bleached kraft pulp of such as coniferous tree, coniferous tree oxygen expose to the open air non-bleached kraft pulp, Coniferous tree bleached kraft pulp is particularly suitable for.

Above-mentioned raw material are mainly made of cellulose, hemicellulose and lignin, wherein the content of lignin is usually 0~40 Quality % or so, particularly 0~10 mass % or so.About these raw material, as needed, the removal that can carry out lignin is To bleaching, the adjustment of lignin amount is carried out.It should be noted that the measurement of lignin content can by Klason method come into Row.

In the cell wall of plant, cellulosic molecule is not unimolecule, but formation rule assemble and gather tens of With crystalline microfibre (fine cellulose fiber), this becomes the basic framework material of plant.Therefore, in order to by above-mentioned original Material manufactures fine cellulose powder, by handling above-mentioned raw material application mashing or pulverization process, high-temperature high-pressure steam, Using the processing of phosphate etc., using N- oxygen radical compound as oxidation catalyst come processing of oxidized fibre cellulose fiber etc., Its fiber is unlocked to the method for nano-scale so as to use.

Among the above, mashing or pulverization process are by applying direct force to raw material such as above-mentioned paper pulp, carrying out mechanical mashing Or the method crushed to unlock fiber to obtain fine cellulose powder.More specifically, such as by the way that paper pulp etc. is utilized High-pressure homogenizer etc. carries out mechanicalness processing, and the cellulose fibre that fibre diameter is unlocked to 0.1~10 μm or so is made 0.1~ The water slurry of 3 mass % or so, and then it is ground to repeatedly using grinder etc. or is melted broken processing, available fibre diameter The fine cellulose powder of 10~100nm or so.

It is above-mentioned grind or melt it is broken processing such as made grinder of chestnut field machinery production " Pure Fine Mill " can be used Etc. carrying out.The grinder is impact, centrifugal force and the shearing force due to raw material by occurring when the gap of upper and lower 2 slice lapping machine And raw material is crushed to the stone mortar formula pulverizer of ultra micron, and can be sheared, be ground simultaneously, micronized, dispersion, emulsification and Fibrillation.In addition, it is above-mentioned grind or melt it is broken processing Zeng Xing Industry Co., Ltd ultra micron grater " Super also can be used Masscolloider " Lai Jinhang.Super Masscolloider be it is a kind of can ultra micro be granulated to being more than simple disintegrating area The grater of domain and the feeling degree to be melted.Super Masscolloider is 2 nothings up and down that can freely adjust interval The ultra micron grater for the stone mortar form that stomata grinding stone is constituted, top grinding stone are to fix, and lower part grinding stone is high speed rotation.Investment The gap of upper metate can be admitted to because of centrifugal force to the raw material of hopper, by resulting powerful compression, shearing and Rotating friction force etc., raw material are gradually grated and are granulated by ultra micro.

In addition, above-mentioned high-temperature high-pressure steam processing is steamed by the way that the raw material such as above-mentioned paper pulp are exposed to high-temperature high pressure water Gas and unlock fiber, thus the method for obtaining fine cellulose powder.

In turn, the above-mentioned processing using phosphate etc. is to carry out phosphate by the surface to raw material such as above-mentioned paper pulp Change, so that the binding force between weakening cellulose fibre, then carries out refiner processing, so that unlocking fiber obtains fine cellulose The facture of powder.For example, the raw material such as above-mentioned paper pulp to be impregnated in the phosphorus of the urea comprising 50 mass % and 32 mass % In the solution of acid, after 60 DEG C penetrate into solution fully between cellulose fibre, phosphorylation, Jiang Qishui are carried out in 180 DEG C of heating After washing, in the aqueous hydrochloric acid solution of 3 mass %, in 60 DEG C hydrolysis process 2 hours, washed again, and then later, in 3 matter In the aqueous sodium carbonate for measuring %, carries out 20 minutes or so handling in room temperature, thus complete phosphorylation, by the processed material with essence Grinding machine defibering, it is hereby achieved that fine cellulose powder.

Moreover, the processing that above-mentioned N- oxygen radical compound is aoxidized cellulose fibre as oxidation catalyst, is After aoxidizing the raw material such as above-mentioned paper pulp, the method for fine cellulose powder is obtained by miniaturization.

It is measured firstly, being scattered in native cellulose fibre using mixing machine etc. with about 10~1000 times of adiabatic drying benchmark In the water of (quality criteria), aqueous dispersions are thus prepared.For becoming the natural fiber of the raw material of above-mentioned fine cellulose fiber Cellulose fiber, for example, wood pulps, wheat straw paper pulp, the bagasse pulp such as coniferous tree system paper pulp, broad leaf tree system paper pulp etc. are non- The cottons system such as timber system paper pulp, cotton linters, cotton linter paper pulp, bacteria cellulose etc..They can be used alone, can also group It closes and uses two or more.In addition, these native cellulose fibres can be implemented with the processing such as mashing for preparatory enlarged surface product.

Then, in above-mentioned aqueous dispersions, use N- oxygen radical compound as oxidation catalyst, carry out native cellulose The oxidation processes of fiber.As the N- oxygen radical compound, such as in addition to TEMPO (2,2,6,6- tetramethyl piperidine-N- oxygen Free radical) except, 4- carboxyl-TEMPO, 4- acetamide-TEMPO, 4- amino-TEMPO, 4- dimethylamino-can also be used TEMPO, 4- phosphono oxygroup-TEMPO, 4- hydroxyl TEMPO, 4- oxygroup TEMPO, 4- methoxyl group TEMPO, 4- (2- acetyl bromide Amine)-TEMPO, 2-aza-adamantane N- oxygen radical etc. be in the C4 TEMPO derivatives etc. with various functional groups.As this The additive amount of a little N- oxygen radical compounds is adequately, usually relative to native cellulose fibre, Ke Yishe with catalytic amount For the range for becoming 0.1~10 mass % in terms of adiabatic drying benchmark.

In the oxidation processes of above-mentioned native cellulose fibre, oxidant and co-oxidants is applied in combination.As oxidant, example Halous acid, hypohalogenous acids can such as be enumerated and cross hydracid and their salt, hydrogen peroxide, cross organic acid, wherein sodium hypochlorite, The alkali metal hypohalite such as sodium hypobromite is suitable.In addition, the alkali bromides such as sodium bromide can be used for example as co-oxidants Metal.The dosage of oxidant is calculated as the model of about 1~100 mass % usually relative to native cellulose fibre with adiabatic drying benchmark It encloses, the dosage of co-oxidants is calculated as the model of about 1~30 mass % usually relative to native cellulose fibre with adiabatic drying benchmark It encloses.

When the oxidation processes of above-mentioned native cellulose fibre, from the viewpoint of being effectively performed oxidation reaction, preferably will The pH of aqueous dispersions maintains 9~12 range.In addition, the temperature of aqueous dispersions when oxidation processes can be at 1~50 DEG C It is arbitrarily set in range, no temperature control can also react at room temperature.As the reaction time, 1~240 minute model can be set to It encloses.It should be noted that in order to make medicament infiltrate into the inside of native cellulose fibre, in order to which more carboxyls are imported fiber Surface can also add penetrant in aqueous dispersions.As penetrant, carboxylate, sulfuric acid, sulfonate, phosphorus can be enumerated Nonionic surfactants such as the anionic systems such as acid esters salt interfacial agent, polyethylene glycol type, polyol type etc..

It is preferred that being removed aqueous dispersions after the oxidation processes of above-mentioned native cellulose fibre, before being miniaturize Contained in the impurity such as unreacted oxidant, various by-products refinement treatment.Specifically, can be used for example repetition into The method of washing and the filtering of the native cellulose fibre for oxidation processes of passing through.The native cellulose fibre obtained after refinement treatment It is usually handled with the state for infiltrating suitable water for miniaturization, as needed, can be dried and threadiness is made Or it is powdered.

Then, for the miniaturization of native cellulose processing, according to expectation, so that the native cellulose through refinement treatment is fine The state that is scattered in water equal solvent is tieed up to carry out.Solvent as decentralized medium used in miniaturization processing, it is usually preferred to Water, according to expectation, also can be used alcohols (methanol, ethyl alcohol, isopropanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, methyl cellosolve, Ethyl cellosolve, ethylene glycol, glycerol etc.), ethers (ethylene glycol dimethyl ether, 1,4- dioxane, tetrahydrofuran etc.), ketone Class (acetone, methyl ethyl ketone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide etc.) etc. is water-soluble Organic solvent, their mixture also can be used.The solid of native cellulose fibre in the dispersion liquid of these solvents at Point concentration is suitably set as 50 mass % or less.If the solid component concentration of native cellulose fibre more than 50 mass %, High energy is needed in dispersion, it is not preferable.It is equal that low pressure homogenizer, high pressure can be used in the miniaturization of native cellulose processing Change device, grinder, shredding machine, ball mill, aeropulverizer, beater, dissociating machine, short screw extruder, double screw extruder, ultrasound The dispersal devices such as wave blender, home-use juicing mixing machine.

The fine cellulose powder handled by miniaturization can be made according to expectation and have adjusted solid component concentration Suspension or dried powdered.Herein, when suspension is made, water can be used only as decentralized medium, Also the mixed solvent of water and other organic solvents, the alcohols such as ethyl alcohol, surfactant, acid, alkali etc. can be used.

It is handled by the oxidation processes of above-mentioned native cellulose fibre and miniaturization, the C6 of the Component units of cellulosic molecule The hydroxyl of position is oxidized to carboxyl by aldehyde-selectivity, can obtain by the content of the carboxyl being 0.1~3mmol/g's The fine cellulose powder of high crystalline that cellulosic molecule is formed, with above-mentioned defined number average fiber diameter.Height knot The fine cellulose powder of crystalline substance has cellulose I type crystalline texture.This means that the fine cellulose powder is with I type The natural cellulosic molecule of being originated from of crystalline texture is surface-oxidised and miniaturize.That is, native cellulose fibre be The fine fiber for being referred to as microfibre produced during its biosynthesis constructs the solid structure of high-order through multi beam, Weaken the strong aggregation force (hydrogen bond between surface) between its microfibre by the importing of aldehyde radical or carboxyl based on oxidation processes, into And passes through miniaturization processing and obtain fine cellulose powder.By adjusting the condition of oxidation processes, increase and decrease the content of carboxyl, Change polarity, or handled by the electrostatic repulsion of carboxyl, miniaturization can control fine cellulose powder avarage fiber diameter, Average fiber length, average aspect ratio etc..

Above-mentioned native cellulose fibre is that I type crystalline texture can be according in the survey for passing through its Wide angle X-ray diffraction image In the diffraction pattern obtained, in two positions of 2 θ=14~17 ° nearby and near 2 θ=22~23 ° there is typical peak to reflect surely It is fixed.In addition, in the cellulosic molecule of fine cellulose powder import carboxyl can by the sample that completely eliminated moisture, There is the absorption (1608cm due to carbonyl in total-reflection type infrared spectroscopy (ATR)^-1Near) confirm.Carboxyl (COOH) In the case of, in 1730cm in said determination^-1There are absorptions.

It should be noted that the native cellulose fibre that halogen atom adheres to or is bonded to after oxidation processes, therefore, for The purpose for removing such residual halogens atom, can also carry out dehalogenate processing.Dehalogenate processing can be by will be at oxidation Native cellulose fibre after reason is impregnated in hydrogenperoxide steam generator, carries out in ozone solution.

Specifically, for example by the native cellulose fibre after oxidation processes in the peroxidating that concentration is 0.1~100g/L It is impregnated in hydrogen solution, with the condition of bath raio 1:5~1:100 or so, preferably 1:10~1:60 or so (mass ratio).Peroxide at this time The concentration for changing hydrogen solution is suitably 1~50g/L, preferably 5~20g/L.In addition, the pH of hydrogenperoxide steam generator be suitably 8~ 11,9.5~10.7 are preferably.

The carboxylic it should be noted that quality relative to the fine cellulose powder for including in aqueous dispersions, in cellulose The amount [mmol/g] of base can be evaluated by the following method.That is, previously prepared 60ml accurate weighing dry mass is micro- 0.5~1 mass % aqueous dispersions of fine cellulose powder sample, after pH is set as about 2.5 using the aqueous hydrochloric acid solution of 0.1M, drop Add the sodium hydrate aqueous solution of 0.05M until pH measures conductivity as about 11.It can be by the slow weak acid of variation of conductivity Neutralization stage in consumed amount of sodium hydroxide (V), determine amount of functional groups using following formula.The amount of functional groups indicates carboxyl Amount.

Amount of functional groups [mmol/g]=V [ml] × 0.05/ fine cellulose powder sample [g]

In addition, fine cellulose powder used in the present invention can be chemically modified and/or physical modification provides It is functional.Herein, it as chemical modification, can carry out by the following method: utilize acetalation, acetylation, cyano ethyl, ether Change, isocyanation esterification Deng Lai addition functional group, or keeps silicate, titanate etc. inorganic using chemical reaction, sol-gal process etc. Object Composite, or cover etc..As the method for chemical modification, for example, will be shaped to the fine cellulose of sheet Powder is impregnated in the method heated in acetic anhydride.In addition it can enumerate, for using N- oxygen radical compound as oxidation Fine cellulose powder obtained from the processing that catalyst aoxidizes cellulose fibre, to the carboxyl in molecule with ion The method of key, amido bond modification amine compounds, quaternary ammonium compound etc..

As the method for physical modification, it can be cited for example that passing through the physical vapor depositions such as vacuum evaporation, ion plating, sputtering Plating methods such as (PVD method), chemical vapor deposition (CVD method), chemical plating, electrolysis plating etc. make the method for metal, ceramic raw material covering.This A little modifications can be for before above-mentioned processing, or after processing.

Fine cellulose powder used in the present invention be threadiness when, it is generally desirable to its avarage fiber diameter be 3nm with Above and it is less than 100nm.The minimum diameter of fine cellulose fiber single fiber is 3nm, therefore can not substantially be manufactured less than 3nm. In addition, if being less than 100nm, even if not being excessively added, can also obtain present invention contemplates that effect, film formation property is also good.It needs Illustrate, the avarage fiber diameter of fine cellulose powder can be carried out according to the measuring method of the size of aforementioned fine powder Measurement.

(Cellulose nanocrystal particle)

The crystal habit that the present inventors is further conceived to fine cellulose powder has made intensive studies, and as a result sends out It is existing, according to cellulosic material hydrolyze to and removed non-crystallized part, only separates the Cellulose nanocrystal particle of crystalline portion, accident Ground is able to solve the above subject, and provides working life also excellent hardening resin composition.

As packing material, the Cellulose nanocrystal particle of crystalline portion is only separated from cellulosic material by being applied in combination With the filler other than the Cellulose nanocrystal particle, so as to provide a kind of hardening resin composition that working life is excellent, It can obtain capable of maintaining low thermal expansion rate and toughness, resistance to the temperature region in the component installation more than 200 DEG C Each characteristic such as hot also excellent solidfied material.

In turn, inventors are conceived to the Cellulose nanocrystal particle that crystalline portion is only separated from cellulosic material, by it Compounding amount has made intensive studies compared with the relationship of coefficient of thermal expansion is with silica, as a result, it has been found that, utilize the cellulose nanometer Brilliant particle can obtain the reducing effect of significant coefficient of thermal expansion with a small amount of compounding amount (referring to Fig. 6-1).

Moreover, inventors have found, by being compounded for ensuring that the insulating materials of the electronic components such as toughness, heat resistance is wanted The fillers such as the silica for each characteristic asked, and be applied in combination and be compounded the Cellulose nanocrystal particle, so as to obtain The distinctive effect of aforementioned present invention (referring to Fig. 6-2,6-3).

In turn, inventors have found that, using the Cellulose nanocrystal particle only formed by crystalline portion, performance can provide The specificity that working life excellent hardening resin composition is such, the fine cellulose powder comprising non-crystallized part is no Effect.

In the present invention, Cellulose nanocrystal particle refers to, as long as by the inorganic acid (salt of cellulosic material high concentration Acid, sulfuric acid, hydrobromic acid etc.) it hydrolyzes and removes non-crystallized part, only separate crystalline portion person, so that it may use any particle.Make For the size of the particle, preferably average crystallite width is 3~70nm, average crystallite length is 100~500nm, more preferably average Crystallization width is 3~50nm, average crystallite length is 100~400nm, and further preferred average crystallite width is 3~10nm, puts down Crystallization length is 100~300nm.Herein, crystallization width refers to that the length of the short side of particle, crystallization length refer to the length of particle The length on side.This Cellulose nanocrystal particle is compared with width, the length particle bigger than its, and the surface area of per unit mass is more Greatly, the ratio of the atom exposed on surface increases.It is therefore contemplated that Cellulose nanocrystal particle can obtain the phase interaction attracted each other With and show reinforcing effect, thermal expansivity reduce.

Herein, the size (average crystallite width, average crystallite length) of Cellulose nanocrystal particle can use SEM (Scanning Electron Microscope；Scanning electron microscope), TEM (Transmission Electron Microscope；Transmission electron microscope), AFM (Atomic Force Microscope；Atomic force microscope) etc. carry out Observation is to measure.

Specifically, the diagonal line in microscope photo is crossed, the measurable particle of positioned adjacent and size is taken out at random 12 points out, after removing maximum particle and the smallest particle, remaining 10 points of the size of measurement (crystallization width, crystallization length), point Not Ping Jun after value be Cellulose nanocrystal particle average crystallite width and average crystallite length.

As Cellulose nanocrystal particle, two or more different person of raw cellulose can be applied in combination.

This Cellulose nanocrystal particle is preferably implemented silicic acid anhydride, uses surface treatment of coupling agent etc..This place The known customary way for being suitable for Cellulose nanocrystal particle can be used in reason.

The compounding amount of Cellulose nanocrystal particle in the present invention is suitble to relative to the total amount for the composition for eliminating solvent For 0.04~30 mass %, it is more suitable for for 0.08~20 mass %, is further adapted for as 0.1~10 mass %.Cellulose nanometer When the compounding amount of brilliant particle is 0.04 mass % or more, the reducing effect of coefficient of thermal expansion can be obtained well.On the other hand, it is When 30 mass % or less, film formation property is improved.

Cellulose nanocrystal particle of the invention can be by by inorganic acid (hydrochloric acid, sulphur of cellulosic material high concentration Acid, hydrobromic acid etc.) it is hydrolyzed and removes non-crystallized part, only crystalline portion is isolated.

Herein, as cellulosic material, the cottons system paper pulp, fiber crops, wheat such as paper paper pulp processed, cotton linter, cotton linters can be enumerated The non-timbers such as grass, bagasse system paper pulp, the cellulose isolated from ascidian, sea grass etc. etc., are not particularly limited.Among these, In The aspect of accessibility, paper paper pulp preferably processed, in terms of it can manufacture the superior CNC of heat resistance, preferably cotton, sea Sheath.

As paper paper pulp processed, broad leaf tree kraft pulp, softwood kraft pulp etc. can be enumerated.

As broad leaf tree kraft pulp, bleached kraft pulp (LBKP), non-bleached kraft pulp (LUKP), oxygen can be enumerated Bleached kraft pulp (LOKP) etc..

As softwood kraft pulp, bleached kraft pulp (NBKP), non-bleached kraft pulp (NUKP), oxygen can be enumerated Bleached kraft pulp (NOKP) etc..

Furthermore it is possible to enumerate chemical pulp, semichemical wood pulp, mechanical pulp, non-wood pulp, using waste paper as raw material De inked pulp etc..As chemical pulp, there are sulfite pulp (SP), soda pulps (AP) etc..As semichemical wood pulp, there is half Chemical pulp (SCP), chemical groundwood pulp (CGP) etc..As mechanical pulp, have photogrammetry pulp mill (GP), thermomechanical pulp (TMP, BCTMP) etc..As non-wood pulp, has and regard small paper mulberry, Edgeworthia chrysantha, fiber crops, mestha etc. as raw material person.

This cellulosic material can be used alone, and can also be mixed with two or more.Alternatively, it is also possible to use machinery Cellulose nano-fibrous (hereinafter also referred to as " CNF ") of the manufactures such as nanofarads, Phosphation method, TEMPO oxidizing process is solved as fine Tie up plain raw material.

Then, the hydrolysis of cellulosic material as described above can carry out as follows: for example utilize sulfuric acid, hydrochloric acid, hydrogen bromine Acid etc. handles the water slurry containing cellulosic material or slurry, or cellulosic material is made directly to be suspended in sulfuric acid, salt It is carried out in the aqueous solutions such as acid, hydrobromic acid.When especially with paper pulp as cellulosic material, crushed using shredding machine, pin stick Machine etc. implements hydrolysis process after the fiber of cotton like is made again, is preferred in terms of being able to carry out uniform hydrolysis process.

In this hydrolysis process, temperature condition is not particularly limited, such as can be set to 25~90 DEG C.In addition, at hydrolysis The condition of reason time is also not particularly limited, such as can be set to 10~120 minutes.

It should be noted that for so by Cellulose nanocrystal particle, example obtained from cellulosic material hydrolysis process Sodium hydroxide alkali such as can be used to be neutralized.

The obtained Cellulose nanocrystal particle, which can according to need, carries out micronized processing.In micronized processing, Processing unit, processing method are not particularly limited.

As micronized processing unit, grinder (stone mortar type pulverizer), high-pressure homogenizer, super-pressure can be used for example Homogenizer, impacting with high pressure type pulverizer, ball mill, ball mill, dish-type refiner, jordan mill, twin screw compounder, vibration Mill, the mixer for well-distribution under high speed rotation, ultrasonic dispersing machine, beater etc..

In micronized processing, preferably water and organic solvent are made alone or in combination diluting Cellulose nanocrystal particle At pulp-like, but it is not particularly limited.As preferred organic solvent, alcohols, ketone, ethers, dimethyl sulfoxide can be enumerated (DMSO), dimethylformamide (DMF) or dimethyl acetamide (DMAc) etc..Decentralized medium can be a kind, or 2 kinds More than.In addition, in decentralized medium comprising other than Cellulose nanocrystal particle solid component, such as the urea with hydrogen bond Even.

In addition, Cellulose nanocrystal particle used in the present invention can be chemically modified and/or physical modification mentions High functionality.Herein, as chemical modification, can use following method and carry out: by acetalation, acetylation, cyano ethyl, Etherificate, isocyanation esterification etc. make functional group's addition, or make the nothings such as silicate, titanate using chemical reaction, sol-gal process etc. The methods of machine object Composite, or cover.As physical modification, can be carried out with plating, vapor deposition.

[filler other than fine powder]

Resin combination of the invention further includes the filler other than above-mentioned fine powder.It, can be with as this filler Enumerate barium sulfate, barium titanate, amorphous silica, crystallinity silica, fused silica, spherical silicon dioxide, cunning The inorganic fillers such as stone, clay, magnesium carbonate, calcium carbonate, aluminium oxide, aluminium hydroxide, silicon nitride, aluminium nitride, titanium oxide.In addition, micro- Can be organic filler when fine powder is Cellulose nanocrystal particle, can be used it is cellulose nano-fibrous as organic filler, Preferred silica in filler.

The average grain diameter of the filler is preferably 3 μm or less, more preferably 1 μm or less.It should be noted that filler is averaged Partial size can be found out by laser diffraction formula particle size distribution analyzer.

The compounding amount of the filler is 1~90 mass %, preferably 2~80 matter in the total amount for the composition for eliminating solvent Measure %, more preferably 5~75 mass %.By the way that the compounding amount of filler to be set as in above range, can ensure to solidify well The film performance of solidfied material afterwards.

Filler other than fine powder and the mix ratio in the total filler of fine powder are by quality ratio (other than fine powder Filler: fine powder)=100:(0.04~30), preferably 100:(0.1~20), more preferably 100:(0.2~10).It is logical It crosses with this mix ratio using filler, is able to maintain that coefficient of thermal expansion is lower, and take into account required by the insulating materials of electronic component Each characteristic such as toughness, heat resistance.

In addition, for the total amount for the filler being compounded in hardening resin composition, preferably according to hardening resin composition Purposes, the requirement characteristic of the insulating materials such as the interlayer dielectic of electronic component, be suitably set as usual known quantities.

< in addition to about first and the 6th purpose fine powder and fine powder other than filler except other with blending together Point >

In first embodiment of the invention, as in addition to about first and the 6th purpose fine powder and fine powder Other compounding ingredients except filler in addition, as described below.

[curable resin]

It in the present invention, as curable resin, is not particularly limited, well known resin can be used, such as can be packet Any material in ingredient containing Thermocurable and photo-curable ingredient, but preferably comprise the material of Thermocurable ingredient.

As Thermocurable ingredient, as long as solidify the resin for showing electrical insulating property by heating, such as can be with There is compound, the melamine resin, organosilicon tree of cyclic ether group using epoxide, oxetane compound etc. Amino resins, polyisocyanate compound, the sealing ends such as rouge, benzoguanamine resin, melamine derivative, benzoguanamine derivative Isocyanate compound, cyclic carbonate compound, episulfide resin, bismaleimide, carbon imidodicarbonic diamide resin, polyamides are sub- Heat-curing resin well known to polyimide resin, polyamide-imide resin, polyphenylene oxide resin, polyphenylene sulfide etc..Particularly preferably At least wantonly a kind of heat cure in molecule with multiple cyclic ether groups and cyclic thioether base (hereinafter referred to as cyclic annular (sulphur) ether) Property resin.Wherein, preferably epoxide, oxetane compound, more preferably as the epoxy resin of epoxide.

As epoxy resin, such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type epoxy tree can be enumerated The bis-phenols type rings such as rouge, bisphenol E-type epoxy resin, bis-phenol M type epoxy resin, bis-phenol p-type epoxy resin, bisphenol Z type epoxy resin Oxygen resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, phenol novolak type epoxy resin, cresol novolac epoxy etc. Phenolic resin varnish type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl-type epoxy resin, aryl alkene type epoxy resin, Four hydroxy phenyl ethane type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, phenoxy group type epoxy resin, bicyclopentadiene Type epoxy resin, norbornene-type epoxy resin, adamantane type epoxy resin, fluorenes type epoxy resin, Glycidyl methacrylate are sweet Grease copolymerization is copolymerization epoxy resin, the epoxy of epoxy resin, N-cyclohexylmaleimide and glycidyl methacrylate Modified polybutadiene rubber derivative, CTBN modified epoxy, trimethylolpropane polyglycidyl ether, phenyl -1,3- Diglycidyl ether, biphenyl -4,4 '-diglycidyl ether, 1,6 hexanediol diglycidylether, ethylene glycol or propylene glycol two Glycidol ether, d-sorbite polyglycidyl ether, three (2,3- glycidyl) isocyanuric acid esters, three (2- hydroxyethyl) isocyanides Urea acid three-glycidyl ester, phenoxy resin etc..

Wherein, it is combined at 40 DEG C and is the solid epoxy of solid-like and is solid-like and at 40 DEG C at 20 DEG C Be down at least either of the semisolid epoxy resin of liquid and at 20 DEG C be liquid liquid epoxies, this is from maintenance Effect of the invention and and then excellent crack resistance when cold cycling in terms of to set out be preferred.As solids epoxy tree The illustration of rouge, semisolid epoxy resin, liquid epoxies can be enumerated and be recorded in Japanese Unexamined Patent Publication 2015-10232 bulletin Substance.

Above-mentioned Thermocurable ingredient is used together with curing agent as needed.As curing agent, can enumerate phenolic resin, Polycarboxylic acids and its acid anhydrides, cyanate ester resin, by acetylation etc. by hydroxy-end capped active ester resin, side chain have carboxyl, Hydroxyl, the cyclic olefin polymer of active ester structure, with there is hydroxyl, carboxyl, activity with a part of said curing property resin The curing agent of the substituent group of the cyclic ether group reaction of ester structure, can be used alone or two or more is applied in combination.

As above-mentioned phenolic resin, phenol resol resins, alkylphenol novolac resin, bisphenol-A can be used Novolac resin, dicyclopentadiene type phenol resin, Xylok type phenolic resin, terpene modified phenolic resin, cresols/naphthols Resin, polyvinylphenols, phenol/naphthol resin, the phenolic resin of the skeleton containing alpha-Naphthol, the cresol novolak tree containing triazine The known resin such as rouge.

Above-mentioned polycarboxylic acids and its acid anhydrides are the compound and its acid anhydrides in a molecule with 2 or more carboxyls, can be enumerated Such as condensation product of the copolymer of (methyl) acrylic acid, the copolymer of maleic anhydride, binary acid etc. and carboxylic acid terminal's acid imide Resin etc. has the resin of carboxylic acid terminal.

Above-mentioned cyanate ester resin is the compound in a molecule with 2 or more cyanic acid ester groups (- OCN).Cyanate ester Resin can be used it is known any one.As cyanate ester resin, for example, phenol novolak type cyanic acid Ester ester resin, alkylphenol phenolic varnish type cyanate ester resin, dicyclopentadiene-type cyanate ester resin, bisphenol A-type cyanic acid Ester ester resin, bisphenol-f type cyanate ester resin, bisphenol S type cyanate ester resin.Alternatively, it is also possible to be a part through triazine Prepolymer.

Above-mentioned active ester resin is not particularly limited, with the resin of 2 or more active ester groups in a preferably molecule.Activity Ester resin usually can by one or more of carboxylic acid compound and thiocarboxylic acid compound, with hydroxy compounds and Thiolation It closes the condensation reaction of one or more of object and obtains.As the active ester resin, the esterification of bicyclopentadiene biphenol can be enumerated Close object, bisphenol-A diacetate esters, diphenyl phthalate, terephthaldehyde's diphenyl phthalate, bis- [4- (the methoxyl group carbonyls of terephthalic acid (TPA) Base) phenyl ester] etc..

It should be noted that the active ester resin be suitable for being reduced relative dielectric constant and dielectric loss angle tangent, Electronic component with low dielectric property.

This heat curable component, curing agent etc. are preferably combined according to using them as the heat-curing resin of constituent The purposes of object, the requirement characteristic of the insulating materials such as the interlayer dielectic of electronic component are suitble to usual well known group At being compounded.

In the present invention, as the hot curing resin composition comprising above-mentioned heat curable component, other than mentioned component, It may include the macromolecule resins such as thermoplastic resin, elastomer, rubber-like particles, imidazolium compounds, amine compounds, hydrazine chemical combination The diluents such as the curing accelerators such as object, phosphorus compound, Striazine derivative, fire retardant, colorant, organic solvent, other additions Agent.

Then, as photo-curable ingredient, as long as to solidify the resin for showing electrical insulating property by light irradiation, it can To enumerate such as (methyl) alkyl-acrylates such as (methyl) 2-EHA, (methyl) cyclohexyl acrylate；(first Base) (methyl) the hydroxyalkyl acrylates class such as acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester；Ethylene glycol, The list of the alkylene oxide derivatives such as propylene glycol, diethylene glycol, dipropylene glycol or two (methyl) esters of acrylic acid；Hexylene glycol, three hydroxyl first The polyalcohols such as base propane, pentaerythrite, two trimethylolpropanes, dipentaerythritol, trihydroxy ethyl isocyanurate or they Ethylene oxide or propylene oxide adduct polynary (methyl) esters of acrylic acid；(methyl) phenoxyethyl acrylate, bisphenol-A The ethylene oxide of phenols or (methyl) esters of acrylic acid of propylene oxide adduct such as polyethoxy two (methyl) acrylate； The glycidol ethers such as glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group isocyanuric acid ester (methyl) esters of acrylic acid；And melamine (methyl) acrylate etc..

Above-mentioned photo-curable ingredient as needed with generate free radicals, wantonly a kind of the photoreaction initiator one in alkali and acid It rises and uses.As the photoreaction initiator, it can be cited for example that double-(2,6- dichloro-benzoyl base) phenyl phosphine oxide, it is double-(2, 6- dichloro-benzoyl base) -2,5- 3,5-dimethylphenyl phosphine oxide, double-(2,6- dichloro-benzoyl base) -4- propylphenylphosphine oxide, Double-(2,6- dichloro-benzoyl base) -1- naphthalene phosphine oxide, double-(2,6- Dimethoxybenzoyl) phenyl phosphine oxide, it is double-(2, 6- Dimethoxybenzoyl) -2,4,4- trimethylpentylphosphine oxide, double-(2,6- Dimethoxybenzoyl) -2,5- diformazan Base phenyl phosphine oxide, double-(2,4,6- trimethylbenzoyl)-phenyl phosphine oxide (BASF JPAN Co. Ltd. system, Double acylphosphine oxide class such as IRGACURE819)；2,6- Dimethoxybenzoyl diphenyl phosphine oxide, 2,6- dichloro-benzoyl Base diphenyl phosphine oxide, 2,4,6- trimethylbenzoyl phenyl phosphinic acid methyl ester, 2- methyl benzoyl diphenyl phosphine oxide, Pivaloyl phenyl phosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF JAPAN Co. Ltd. system, The monoacylphosphine oxides phosphine such as DAROCURTPO)；1- hydroxy-cyciohexyl phenyl ketone, 1- [4- (2- hydroxyl-oxethyl)-phenyl] -2- Hydroxy-2-methyl -1- acetone, 2- hydroxyl -1- { 4- [4- (2- hydroxy-2-methyl-propiono)-benzyl] phenyl } -2- methyl-the third The hydroxy acetophenones classes such as alkane -1- ketone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone；Benzoin, benzoyl, benzoin methyl The benzoin class such as ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether；Benzoin Alkyl ether；Benzophenone, to methyl benzophenone, Michler's keton, methyl benzophenone, 4,4 '-dichloro benzophenones, 4,4 '- The benzophenones such as double diethylamino benzophenone；Acetophenone, 2,2- dimethoxy -2- phenyl acetophenone, 2,2- diethoxy Base-2- phenyl acetophenone, 1,1- dichloroacetophenone, 1- hydroxycyclohexylphenylketone, 2- methyl-1-[4- (methyl mercapto) phenyl]- 2- morpholinyl -1- acetone, 2- benzyl -2- dimethylamino -1- (4- morpholino phenyl) -1- butanone, N, N- dimethylamino benzene The acetophenones such as ethyl ketone；Thioxanthones, 2- ethyl thioxanthones, 2-isopropylthioxanthone, 2,4- dimethyl thioxanthone, 2,4- diethyl The thioxanthene ketone class such as thioxanthones, 2-chlorothioxanthone, 2,4- diisopropylthioxanthone；Anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2- ethyl The Anthraquinones such as anthraquinone, 2- tert-butyl anthraquinone, 1- chloroanthraquinone, 2- amyl anthraquinone, 2- amino anthraquinones；Acetophenone dimethyl ketal, benzene The ketals classes such as even acyl dimethyl ketal；Ethyl 4-dimethylaminobenzoate, 2- (dimethylamino) ethylamino benzonitrile acid esters, to two The benzoates such as methylbenzoic acid ethyl ester；{ 1- [4- (thiophenyl) -2- (O- benzoyl oxime)] } 1,2- acetyl caproyl, 1- [9- second Base -6- (2- methyl benzoyl) -9H- carbazole -3- base] the oximes esters such as -1- (O- acetyl oxime) ethyl ketone；Bis- (η 5-2,4- rings penta 2 Alkene -1- base)-bis- (the fluoro- 3- of 2,6- bis- (1H- pyrroles -1- base) phenyl) titaniums, bis- (cyclopentadiene)-bis- [fluoro- 3- (2- of 2,6- bis- (1- pyrroles -1- base) ethyl) phenyl] the luxuriant titanium class such as titanium；Curing phenyl 2- nitrofluorene, butyroin, anisoin ethyl ether, idol Nitrogen double isobutyronitrile, tetramethylthiuram disulfides etc..Above photoreaction initiator can be used alone, can also group It closes and uses two or more.

This photocuring ingredient, photoreaction initiator etc. are preferably according to using them as the light-cured resin of constituent The purposes of composition, the requirement characteristic of the insulating materials such as the interlayer dielectic of electronic component are suitable for known in usual Composition be compounded.

In the present invention, as the Photocurable resin composition comprising above-mentioned photocuring ingredient, other than mentioned component, Also macromolecule resins such as thermoplastic resin, elastomer, rubber-like particles, sensitizer, fire retardant, colorant, organic be may include The diluents such as solvent, other additives.

In addition, using hardening resin composition of the invention as the light for the alkali developable that can be developed with aqueous alkali Solder mask composition further uses tree containing carboxyl in use, it is preferred that in addition to above-mentioned heat curable component and point other than be light-cured into Rouge.

(containing carboxy resin)

As carboxy resin is contained, it can be used and contain carboxyl with 1 or more the photosensitive of photosensitive unsaturated double-bond Resin and without photosensitive unsaturated double-bond any one of containing carboxy resin, be not particularly limited.As containing carboxylic Base resin, can be particularly preferably using the resin being exemplified below.

(1) contain carboxy resin as obtained from the copolymerization of unsaturated carboxylic acid and compound with unsaturated double-bond, and Be modified and adjust molecular weight, acid value containing carboxy resin.

(2) make containing unsaturated with oxirane ring and olefinic in carboxyl (methyl) acrylic copolymer resin and 1 molecule It is photosensitive obtained from the compound reaction of group to contain carboxy resin.

(3) make compound and with unsaturated double-bondization that 1 epoxy group and unsaturated double-bond are respectively provided in 1 molecule The copolymer for closing object is reacted with unsaturated monocarboxylic, keeps the secondary hydroxyl generated by the reaction and saturation or unsaturated multi-anhydride anti- It is photosensitive obtained from answering to contain carboxy resin.

(4) after reacting hydroxyl polymer-containing with saturation or unsaturated multi-anhydride, make the carboxylic acid generated by the reaction and 1 Photosensitive hydroxyl obtained from the compound reaction of 1 epoxy group and unsaturated double-bond and carboxyl are respectively provided in molecule Resin.

(5) it reacts multi-functional epoxy compound with unsaturated monocarboxylic, makes one of the secondary hydroxyl generated by the reaction It is photosensitive containing carboxy resin obtained from dividing or all being reacted with multi-anhydride.

(6) make to have in multi-functional epoxy compound and 1 molecule 2 or more hydroxyls and with other than the hydroxyl of epoxy reaction The compound of 1 reactive group reacted with the monocarboxylic acid containing unsaturated group, keep resulting reaction product and multi-anhydride anti- Photoresist containing carboxyl obtained from answering.

(7) make the reaction product of the resin with phenolic hydroxyl group and alkylene oxide or cyclic carbonate with containing unsaturated group Monocarboxylic acid reaction, photoresist containing carboxyl obtained from reacting resulting reaction product with multi-anhydride.

(8) make the chemical combination in multi-functional epoxy compound and 1 molecule at least one alcohol hydroxyl group and 1 phenolic hydroxyl group Object is reacted with the monocarboxylic acid containing unsaturated group, make the alcohol hydroxyl group of resulting reaction product reacted with the anhydride group of multi-anhydride and Obtained photoresist containing carboxyl.

This is containing carboxy resin preferably using the solidification by the resin as alkali developables such as the solder mask compositions of constituent Usual well known composition is compounded in property resin combination.

In the hardening resin composition of present invention mentioned above, according to its purposes, and then can suitably it be compounded usual Other compounding ingredients.As other usual compounding ingredients, such as described above, thermoplastic resin, elasticity can be enumerated The diluents such as the macromolecule resins such as body, rubber-like particles, curing accelerator, sensitizer, fire retardant, colorant, organic solvent, its It is his additive, specifically usual known in defoaming agent levelling agent, thixotropy conferring agents thickener, coupling agent, dispersing agent etc. Additive etc..

Particularly as colorant, the usual well known colorant such as red, blue, green, yellow can be used, face also can be used Material, dyestuff, pigment it is any number of.It is preferably not halogen but from the viewpoint of reduction carrying capacity of environment and to the influence of human body Element.

Red stain:

As red stain, can enumerate monoazo system, diazonium system, azo lake system, benzimidazolone system, be, Diketopyrrolo-pyrrole system, condensation azo system, anthraquinone system, quinacridone etc..

Blue colorant, green colourant:

As blue colorant, green colourant, there are phthalocyanine system, anthraquinone system, pigment system can enumerate and be classified as pigment (Pigment) compound, specifically, having color index (C.I.；Dyeing and dyer Association of Engineers (The Society Of Dyers and Colourists) distribution) number compound.In addition it is also possible to the phthalein substituted or unsubstituted using metal Cyanine compound.

Yellow colorants:

As yellow colorants, monoazo system, diazonium system, condensation azo system, benzimidazolone system, iso-indoles can be enumerated Quinoline ketone system, anthraquinone system etc..

In addition, the colorants such as purple, orange, dark brown, black can be added for the purpose of adjustment tone.

The specific compounding ratio of colorant can by using type, other additives of colorant etc. type it is suitable Work as adjustment.

As organic solvent, the ketones such as methyl ethyl ketone, cyclohexanone can be enumerated；The virtues such as toluene, dimethylbenzene, durol Fragrant race's hydro carbons；Methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl The glycol ethers such as ether, diethylene glycol monoethyl ether, dihydroxypropane single-ethyl ether, triethylene glycol monoethyl ether；Ethyl acetate, acetic acid The esters such as carboxylate of butyl ester, cellosolve acetate, diethylene glycol monoethyl ether acetic acid esters and above-mentioned glycol ethers；Ethyl alcohol, propyl alcohol, The alcohols such as ethylene glycol, propylene glycol；The aliphatic hydrocarbons such as octane, decane；Petroleum ether, naphtha, non-hydrogenated petroleum brain, solvent naphtha Equal petroleum series solvent etc..

Hardening resin composition of the invention comprising ingredient as described above can carry out dry film come using, It can directly use in fluid form.It should be noted that in fluid form in use, can may be 2 for 1 liquid type It is more than liquid type.

It is set to be coated with or even be infiltrated in glass cloth, glass in addition, hardening resin composition of the invention can also be used as And the sheet-like fibers matter substrate such as non-woven fabrics of aromatic polyamides carry out semi-solid preparation, so-called prepreg come using.

Dry film of the invention has by being coated on hardening resin composition of the invention in film (support film) And resin layer obtained from drying.

Herein, when forming dry film, hardening resin composition of the invention with above-mentioned organic solvent diluting and is adjusted first It is whole for after viscosity appropriate, using comma coater, knife type coater, lip type coating machine, bar coating machine, extrusion coated machine, Reverse coating machine, transfer roll-coater, gravure coater, Bracewell coater etc. on film with the coating of uniform thickness.Later, By the composition after coating usually in 40~130 DEG C of at a temperature of progress drying in 1~30 minute, it is possible thereby to form resin layer. Coating film thickness is not particularly limited, in general, being fitted with the film thickness gauge after drying in 3~150 μm, the range preferably at 5~60 μm Preferably select.

As above-mentioned film (support film), resin film can be used, poly terephthalic acid second two can be used for example The polyester films such as alcohol ester (PET), Kapton, polyamidoimide film, polypropylene film, polystyrene film etc.. The thickness of film is not particularly limited, is usually suitable for selection in the range of 10~150 μm.More preferably 15~130 μm Range.

For being thusly-formed the film of the resin layer formed by hardening resin composition of the invention, for preventing ash Dirt is attached to the purpose on the surface of resin layer, and peelable film (protective film) preferably and then in resin layer surface is laminated.

As the peelable film, as long as in removing and the bonding force of resin layer is less than resin layer and support film Polyethylene film, polytetrafluoroethylene film, polypropylene film, surface treated paper etc. can be used for example in bonding force.

Solidfied material of the invention is will be in the hardening resin composition of aforementioned present invention or the dry film of aforementioned present invention Made of resin layer solidification.This solidfied material of the invention can be suitable for as requiring solder resist, the interlayer of insulating reliability exhausted The electronic part material of edge material, filling perforation material etc. uses.

Electronic component of the invention has the solidfied material of aforementioned present invention, specifically, printed circuit board etc. can be enumerated. It, can especially by the hardening resin composition of aforementioned present invention is used as the multilayer board of interlayer dielectic With the insulating reliability with good interlayer.

The other except < filler other than about the fine powder and fine powder of the second~the 5th purpose are with blending together Point >

In first embodiment of the invention, as in addition to the fine powder and fine powder about the second~the 5th purpose Other compounding ingredients except filler in addition, as described below.

About the second object of the present invention, hardening resin composition of the invention is preferably comprised with naphthalene skeleton and anthracene bone At least wantonly a kind of cyclic ether compound in frame is as curable resin.

In this way, stacking is made by using with the cyclic ether compound of at least any one in naphthalene skeleton and anthracene skeleton When the electronic component of structure, it is able to suppress interlayer migration, it is hereby achieved that the insulating reliability of good interlayer.Especially from It sets out in terms of being easy to happen migration using the surface that de-smear handles the roughened insulating layer of progress, is easy in this case Ensure that the aspect of the insulating reliability of interlayer, the present invention are useful.

In addition, by the reducing effect of compounding fine powder bring thermal expansivity, the hydrophily person in fine powder It can show significantly.This fine powder is big to the quantum effect of optical electrical resistance magnetism, therefore reactivity, electrical property Etc. physical property variation, it may occur however that unexpected variation.When thinking to be made this time electronic component of such stepped construction, interlayer Insulating reliability difference be for this reason that.Fine powder is hydrophilic particle as such as fine cellulose fiber When, the migration of interlayer becomes particularly poor.In this regard, by using the ring-type at least any one in naphthalene skeleton and anthracene skeleton Ether compound can solve.

[at least wantonly a kind of the cyclic ether compound with naphthalene skeleton and anthracene skeleton]

Cyclic ether compound with naphthalene skeleton is the structure with naphthalene skeleton or from naphthalene skeleton and has cyclic ether Compound.Cyclic ether compound with naphthalene skeleton is not particularly limited, with the change of 2 or more cyclic ethers in preferably 1 molecule Close object.The cyclic ether can be cyclic thioether.

As commercially available product, Epiclon HP-4032, HP-4032D, HP-4700, HP-4770, HP-5000 can be enumerated (being Dainippon Ink Chemicals's system), NC-7000L, NC-7300L, NC-7700L (being Nippon Kayaku K. K's system), ZX- 1355, ESN-155, ESN-185V, ESN-175, ESN-355, ESN-375, ESN-475V, ESN-485 (are that gold is lived by Nippon Steel Chemical Co., Ltd. system) etc..

Cyclic ether compound with anthracene skeleton is the structure with anthracene skeleton or from anthracene skeleton and has cyclic ether Compound.Cyclic ether compound with anthracene skeleton is not particularly limited, with the change of 2 or more cyclic ethers in preferably 1 molecule Close object.The cyclic ether can be cyclic thioether.

As commercially available product, YX-8800 (Mitsubishi chemical Co., Ltd's system) etc. can be enumerated.

The compounding amount of at least wantonly a kind of cyclic ether compound with naphthalene skeleton and anthracene skeleton is relative to eliminating solvent The total amount of composition, preferably 0.5 mass % or more and 80 mass % or less, more preferably 1 mass % or more and 40 mass % It below, is more preferably 1.5 mass % or more and 30 mass % or less.The compounding amount of above-mentioned cyclic ether compound is 0.5 matter When measuring % or more, the reduction of the insulating reliability of the interlayer due to fine cellulose fiber can be prevented.It on the other hand, is 80 When quality % or less, curability is improved.

In the present invention, above-mentioned at least wantonly a kind of the cyclic ether compound with naphthalene skeleton and anthracene skeleton has as solidification The function of property resin, the cyclic ether compound with naphthalene skeleton and the cyclic ether compound with anthracene skeleton can individually make With can also be applied in combination.

In the present invention, and then according to expectation, at least wantonly a kind of the ring-type with naphthalene skeleton and anthracene skeleton can be applied in combination The curable resins such as heat-curing resin, light-cured resin other than ether compound.

About the third object of the present invention, hardening resin composition of the invention is preferably comprised selected from by having two rings penta At least one kind of conduct in the group of the cyclic ether compound of diene skeleton and the phenolic resin composition with bicyclopentadiene skeleton Curable resin.

In this way, by using selected from by the cyclic ether compound with bicyclopentadiene skeleton and with bicyclopentadiene bone It is at least one kind of in the group of the phenolic resin composition of frame, relative dielectric constant and dielectric loss angle tangent can be reduced, it is available Electronic component with low dielectric property.On the other hand, by using fine powder, it can be ensured that solidfied material with it is copper-plated closely sealed Property, it is capable of forming the circuit of fine.

In addition, fine powder used in the present invention has the bicyclopentadiene bone low with copper-plated adaptation by compounding The curable resin of frame, the solidfied material of the composition comprising the curable resin can obtain it is very high with it is copper-plated closely sealed Property.In addition, the effect is obtained while the dielectric property from bicyclopentadiene skeleton can not be reduced.

[cyclic ether compound with bicyclopentadiene skeleton and the phenolic resin with bicyclopentadiene skeleton]

Cyclic ether compound with bicyclopentadiene skeleton is with bicyclopentadiene skeleton or to be originated from bicyclopentadiene The structure of skeleton and the compound with cyclic ether.Cyclic ether compound with bicyclopentadiene skeleton is not particularly limited, It is preferred that having 2 or more cyclic ether persons in 1 molecule.The cyclic ether can be cyclic thioether.

As commercially available product, Epiclon HP-7200 can be enumerated, HP-7200H, HP-7200L (are Dainippon Ink Chemicals System), XD-1000-1L, XD-1000-2L (being Nippon Kayaku K. K's system), Tactix558, Tactix756 (be Huntsman Advanced Materials corporation) etc..

Phenolic resin with bicyclopentadiene skeleton is with bicyclopentadiene skeleton or to be originated from bicyclopentadiene skeleton Structure and with phenolic hydroxyl group compound.Phenolic resin with bicyclopentadiene skeleton is not particularly limited, and preferably 1 There is 2 or more phenolic hydroxyl group persons in molecule.As commercially available product, Resitop GDP-6085, Resitop can be enumerated GDP-6095LR、Resitop GDP-6095HR、Resitop GDP-6115L、Resitop GDP-6115H、Resitop GDP-6140 (being Gunsaka Chem. Industry Co., Ltd.'s system), J-DPP-95, J-DPP-115 (being JFE chemical company system) etc..

Selected from by the cyclic ether compound with bicyclopentadiene skeleton and the phenolic resin with bicyclopentadiene skeleton Total amount of at least one kind of compounding amount relative to the composition for eliminating solvent in the group of composition, preferably 0.5 mass % or more and 80 mass % or less, more preferably 1 mass % or more and 40 mass % or less, further preferably 1.5 mass % or more and 30 Quality % or less.Selected from by the cyclic ether compound with bicyclopentadiene skeleton and with the phenolic aldehyde tree of bicyclopentadiene skeleton When at least one kind of compounding amount in the group of rouge composition is 0.5 mass % or more, low dielectric property can be obtained well.It is another Aspect, when being 80 mass % or less, curability is improved.

It is above-mentioned selected from by the cyclic ether compound with bicyclopentadiene skeleton and with bicyclopentadiene bone in the present invention At least one kind of function having as curable resin in the group of the phenolic resin composition of frame, can use individually has The cyclic ether compound of bicyclopentadiene skeleton can also be applied in combination with the phenolic resin of bicyclopentadiene skeleton.

In the present invention, and then according to expectation, it can be applied in combination selected from by the ring-type etherificate with bicyclopentadiene skeleton Close object and with bicyclopentadiene skeleton phenolic resin composition group in it is at least one kind of other than heat-curing resin, light it is solid The curable resins such as the property changed resin.

About the fourth object of the present invention, hardening resin composition of the invention preferably comprises phenoxy resin as solid The property changed resin.

In this way, de-smear can be gone in de-smear process with the short time by using phenoxy resin and fine powder, And the surface roughness of solidfied material can be suppressed to smaller, therefore it can efficiently transmit high-frequency.On the other hand, even if table Surface roughness is small, also ensures that solidfied material and copper-plated adaptation, therefore is capable of forming the circuit of fine.

In addition, the solidfied material of the composition comprising the fine powder can hold by using fine powder of the invention It changes places de-smear, while the surface roughness for being able to suppress solidfied material is smaller and ensures and copper-plated adaptation.The effect It is to be shown by the combination with aftermentioned phenoxy resin.Even if in addition, effect hydroaropic substance in fine powder Also it can show significantly.

[phenoxy resin]

Phenoxy resin is usually to be synthesized by bisphenols with epoxychloropropane.The bisphenols used has bisphenol A-type, bis-phenol F type, bisphenol S type, biphenyl type, bis-phenol acetophenone type, fluorenes type, trimethyl-cyclohexane type, terpenes type etc., and then also have these 2 Kind or more copoly type.Phenoxy resin is not particularly limited, and when as Photocurable composition, is desired for end epoxy Type.As commercially available product, can enumerate 1256,4250,4275, YX8100, YX6954, YL7213, YL7290, YL7482 (be Mitsubishi chemical Co., Ltd's system), FX280, FX293, YP50, YP50S, YP55, YP70, YPB-43C (be that aurification is lived by Nippon Steel Learn Co. Ltd. system), PKHB, PKHC, PKHH, PKHJ, PKFE, PKHP-200, PKCP-80 (being InChem corporation) etc..

Total amount of the compounding amount of phenoxy resin relative to the composition for eliminating solvent, preferably 0.1 mass % or more And 50 below mass %, more preferably 0.3 mass % or more and 30 mass % or less, further preferably 0.5 mass % or more And 10 below mass %.When the compounding amount of phenoxy resin is 0.1 mass % or more, due to the removal of the glue residue of fine powder Property and conductor adaptation improve.On the other hand, for 50 below the mass when, curability improve.

In the present invention, according to expectation, it can be further combined solid using heat-curing resin, the light other than phenoxy resin The curable resins such as the property changed resin.

About the fifth object of the present invention, hardening resin composition of the invention is preferably comprised selected from by with biphenyl bone It is at least one kind of as curable resin in the group of the cyclic ether compound of frame and the phenolic resin composition with biphenyl backbone.

In this way, by using selected from by the cyclic ether compound with biphenyl backbone and with the phenolic resin of biphenyl backbone It is at least one kind of in the group of composition, when forming copper facing on solidfied material with solid shape, it is able to suppress the thermal history because of component installation etc. And copper facing generates expansion.

In addition, by the reducing effect of compounding fine powder bring thermal expansivity, even if the hydrophily in fine powder Substance show also significantly.On the other hand, when fine powder is, for example, hydrophilic particle as fine cellulose fiber, It is especially considering that the expansion being easy to produce at a high temperature of the copper facing of aforementioned solid shape, therefore application of the invention is useful.

[in the group being made of the cyclic ether compound with biphenyl backbone and the phenolic resin with biphenyl backbone It is at least one kind of]

Cyclic ether compound with biphenyl backbone is the structure with biphenyl backbone or from biphenyl backbone and has ring The compound of shape ether.Cyclic ether compound with biphenyl backbone is not particularly limited, and has 2 or more rings in preferably 1 molecule The compound of shape ether.The cyclic ether can be cyclic thioether.

As commercially available product, can enumerate NC-3000H, NC-3000L, NC-3100 (being Nippon Kayaku K. K's system), YX-4000, YX4000H, YL-6121 (being Mitsubishi chemical Co., Ltd's system), Denacol EX-412 (Nagase ChemteX Co. Ltd. system) etc..

The compounding amount of cyclic ether compound with biphenyl backbone is relative to the total amount for eliminating solvent, preferably 0.5 matter Amount % or more and 80 mass % or less, more preferably 1 mass % or more and 40 mass % or less, further preferably 1.5 matter Measure % or more and 30 mass % or less.When the compounding amount of above compound is 0.5 mass % or more, it can prevent due to fine The copper-plated expansion of particle.On the other hand, be 80 mass % or less when, curability improve.

Phenolic resin with biphenyl backbone is the structure with biphenyl backbone or from biphenyl backbone and has phenol hydroxyl The compound of base.Phenolic resin with biphenyl backbone is not particularly limited, and has 2 or more phenolic hydroxyl group in preferably 1 molecule Person.As commercially available product, GPH-65, GPH-103 (Nippon Kayaku K. K's system), MEH-7851SS, MEH- can be enumerated 7851M, MEH-7851-4H, MEH-7851-3H (bright and chemical conversion Co. Ltd. system), HE200 (Air Water Co. Ltd. system) Deng.

The compounding amount of phenolic resin with biphenyl backbone is relative to the total amount for eliminating solvent, preferably 0.5 matter Measure % or more and 60 mass % or less, more preferably 1 mass % or more and 30 mass % or less, further preferred 1.5 mass % Above and 20 mass % or less.When the compounding amount of above compound is 0.5 mass % or more, it can prevent due to subparticle Copper-plated expansion.On the other hand, be 60 mass % or less when, curability improve.

It is above-mentioned selected from by the cyclic ether compound with biphenyl backbone and with the phenolic resin of biphenyl backbone in the present invention At least one kind of function having as curable resin in the group of composition, has the cyclic ether compound of biphenyl backbone and has The phenolic resin of biphenyl backbone can use individually, and can also be applied in combination.

In the present invention, according to expectation, it can be further combined using selected from by the cyclic ether compound with biphenyl backbone And heat-curing resin, light-cured resin etc. other than at least one kind of in the group of the phenolic resin composition with biphenyl backbone Curable resin.

(heat-curing resin)

As heat-curing resin, as long as solidifying the resin to show electrical insulating property by heating, such as can To enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol E-type epoxy resin, bis-phenol M type The bisphenol-type epoxy resins such as epoxy resin, bis-phenol p-type epoxy resin, bisphenol Z type epoxy resin, bisphenol A novolac type ring oxygen The phenolic resin varnish type epoxy resins such as resin, phenol novolak type epoxy resin, cresol novolac epoxy, biphenyl type ring Oxygen resin, biphenyl aralkyl-type epoxy resin, aryl alkene type epoxy resin, four hydroxy phenyl ethane type epoxy resin, benzene oxygen Type epoxy resin, dicyclopentadiene-type epoxy resin, norbornene-type epoxy resin, adamantane type epoxy resin, fluorenes type ring Oxygen resin, glycidyl methacrylate copolymerization are that epoxy resin, N-cyclohexylmaleimide and Glycidyl methacrylate are sweet The copolymerization epoxy resin, epoxy-modified polybutadiene rubber derivative, CTBN modified epoxy, trimethylolpropane of grease Polyglycidyl ether, phenyl -1,3- diglycidyl ether, biphenyl -4,4 '-diglycidyl ether, 1,6-HD two shrink sweet Oily ether, the diglycidyl ether of ethylene glycol or propylene glycol, d-sorbite polyglycidyl ether, three (2,3- glycidyl) isocyanide ureas Acid esters, triglycidyl group three (2- hydroxyethyl) isocyanuric acid ester, phenol resol resins, cresol novolac resin, The novolak phenolics such as bisphenol A novolac resin, unmodified resol, with tung oil, linseed oil, core Phenolic resin, phenoxy resin, the urine such as the resol type phenol resins such as the modified resol of the oil that peach oil etc. is modified Resin, unsaturated polyester resin, bimaleimide resin, the adjacent benzene containing triazine ring such as plain (urea) resin, melamine resin Dioctyl phthalate diallyl phthalate resin, organic siliconresin, the resin with benzoxazine ring, norbornene resin, cyanate ester resin, Isocyanate resin, carbamate resins, benzocyclobutane olefine resin, maleimide resin, Bismaleimide Triazine tree Rouge, poly methylene imine resin, Thermocurable polyimides, bicyclopentadiene biphenol ester compounds, bisphenol-A diacetate esters, adjacent benzene Bis- [4- (methoxycarbonyl) phenyl ester] the isoreactivity ester compounds of diformazan diphenyl phthalate, terephthaldehyde's diphenyl phthalate, terephthalic acid (TPA) Deng.Wherein, it if using active ester compound, can reduce the thermal expansion in high-temperature area, can ensure that well low-heat is swollen Swollen rate, therefore it is preferred that.

(light-cured resin (free radical polymerization))

As the light-cured resin, as long as solidifying the tree of display electrical insulating property by active energy beam irradiation Rouge, especially can it is preferable to use in molecule with 1 or more ethylenic unsaturated bond compound.As with olefinic insatiable hunger With the compound of key, known usual optical polymerism oligomer and optical polymerism vinyl monomer etc. can be used.

As optical polymerism oligomer, unsaturated polyester system oligomer, (methyl) acrylic ester oligomer can be enumerated Deng.As (methyl) acrylic ester oligomer, phenol Novolac epoxy (methyl) acrylate, cresol novolac can be enumerated Epoxies (methyl) acrylate, carbamic acid such as novalac epoxy (methyl) acrylate, biphenol type epoxy (methyl) acrylate Ester (methyl) acrylate, epoxy amino formic acid esters (methyl) acrylate, polyester (methyl) acrylate, polyethers (methyl) third Olefin(e) acid ester, polybutadiene-modified (methyl) acrylate etc..It should be noted that in this specification, (methyl) acrylate is The term of general name acrylate, methacrylate and their mixture, it is also the same about other similar performance.

As optical polymerism vinyl monomer, known usual substance can be enumerated, such as styrene, chlorobenzene second can be enumerated The styrene derivatives such as alkene, α-methylstyrene；The vinyl esters such as vinyl acetate, butyric acid vinyl acetate or vinyl benzoate Class；Vinyl isobutyl ether, vinyl n-butyl ether, vinyl tertbutyl ether, vinyl n-pentyl ether, vinyl isopentyl Ether, vinyl n-octadecane base ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ethers, triethylene glycol monomethyl ethylene The vinyl ethers such as base ether；Acrylamide, Methacrylamide, N- hydroxymethylacrylamide, N- hydroxymethyl metering system (methyl) third such as amide, N- methoxy acrylamide, N- ethoxymethyl acrylamide, N- butoxy methyl acrylamide Acrylamide；The allyls chemical combination such as Triallyl isocyanurate, diallyl phthalate, diallyl isophthalate Object；(methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) propylene The esters of (methyl) acrylic acid such as sour isobornyl thiocyanoacetate, (methyl) phenyl acrylate, (methyl) phenoxyethyl acrylate；(methyl) (methyl) the acrylic acid hydroxyls such as Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, pentaerythrite three (methyl) acrylate Base alkyl esters；The alkoxyalkylenes glycol lists such as (methyl) methoxyethyl acrylate, (methyl) ethoxyethyl acrylate (methyl) esters of acrylic acid；Ethylene glycol two (methyl) acrylate, butanediol two (methyl) esters of acrylic acid, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, Ji Wusi Poly- (methyl) acrylate of the alkylidene polyols such as alcohol four (methyl) acrylate, dipentaerythritol six (methyl) acrylate； Diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, three propylene of ethoxylated trimethylolpropane Poly- (methyl) esters of acrylic acid of the polyether polyols such as acid esters, propoxylation trimethylolpropane tris (methyl) acrylate； Poly- (methyl) esters of acrylic acid such as 3-hydroxypivalic acid neopentyl glycol ester two (methyl) acrylate；Three [(methyl) acryloxies Ethyl] poly- (methyl) esters of acrylic acid of isocyanurate types such as isocyanuric acid ester etc..

(light-cured resin (cationic polymerization))

It can be suitable for using alicyclic ring epoxy compound, oxetane compound and second as the light-cured resin Alkenyl ether compound etc..Wherein, as alicyclic ring epoxy compound, 3,4,3 ', 4 '-diepoxy dicyclohexyls, 2,2- can be enumerated Bis- (3,4- the epoxycyclohexyl) -1,3- hexafluoropropane of bis- (3,4- epoxycyclohexyl) propane, 2,2-, bis- (3,4- epoxycyclohexyls) Methane, 1- [1,1- bis- (3,4- epoxycyclohexyls)] ethylo benzene, bis- (3,4- epoxycyclohexyl) adipate esters, 3,4- epoxy hexamethylene Ylmethyl (3,4- epoxy) cyclohexane carboxylate, (3,4- epoxy -6- methylcyclohexyl) methyl -3 ', 4 '-epoxy -6- methyl rings Bis- (the 3,4- 7-oxa-bicyclo[4.1.0 carboxylic acid) esters of cyclohexane carboxylic-acid ester, ethylidene -1,2-, 7-oxa-bicyclo[4.1.0,3,4- epoxycyclohexyl-methyl Alcohol, 3,4- epoxycyclohexylethyl trimethoxy silane etc. have the alicyclic ring epoxy compound etc. of epoxy group.As commercially available product, example Celloxide 2000, the Celloxide 2021, Celloxide of Daicel chemical industry Co. Ltd. system can such as be enumerated 3000,EHPE3150；The Epomic VG-3101 of Mitsui Chemicals, Inc；Oiling Shell Epoxy Co. Ltd. system E-1031S；TETRAD-X, TETRAD-C of Mitsubishi Gas Chemical Co., Ltd；The EPB-13 of Tso Tat Co., Ltd., Japan, EPB-27 etc..

As oxetane compound, can enumerate bis- [(3- methyl -3- oxetanylmethoxy) methyl] ethers, Bis- [(3- ethyl -3- oxetanylmethoxy) methyl] ethers, 1,4- bis- [(3- methyl -3- oxetanylmethoxies) Methyl] benzene, bis- [(3- ethyl -3- oxetanylmethoxy) methyl] benzene of 1,4-, acrylic acid (3- methyl -3- oxa- ring fourth Alkyl) methyl esters, acrylic acid (3- ethyl -3- oxetanyl) methyl esters, methacrylic acid (3- methyl -3- oxetanyl) The multifunctional oxa- rings such as methyl esters, methacrylic acid (3- ethyl -3- oxetanyl) methyl esters, their oligomer or copolymer Butanes and oxetanes alcohol and novolac resin, poly- (4-Vinyl phenol), Cardo type bisphenols, calixarenes The etherates of resin with hydroxyl such as class, resorcinol calixarene kind or silsesquioxane, with oxetanes ring not It is saturated the oxetane compounds such as the copolymer of monomer and (methyl) alkyl acrylate.As commercially available product, such as can lift Eternacoll OXBP, OXMA, OXBP, EHO, xyxylene dioxygen azetidine, East Asia of Ube Industries, Ltd out Synthesize Aron oxetane OXT-101 of Co. Ltd. system, OXT-201, OXT-211, OXT-221, OXT-212, OXT-610, PNOX-1009 etc..

As vinyl ether compound, isobide divinyl ether, oxanorbornene divinyl ether can be enumerated Deng cyclic annular ether type vinyl ethers (vinyl ethers that oxirane ring, oxetanes ring, butyl oxide link etc. have cyclic ether group)；Benzene The vinyl aryl ethers such as base vinyl ethers；The alkyl vinyl ethers such as n-butyl vinyl ether, octyl vinyl ether；Cyclohexyl. vinyl The cycloalkyl vinyl ethers such as base ether；Hydroquinone divinyl ether, 1,4- butanediol divinyl ether, hexamethylene divinyl Polyfunctional vinyls ether, α and/or β, ether, cyclohexanedimethanol divinyl base ether etc. with substituent groups such as alkyl, allyls Vinyl ether compound etc..As commercially available product, it can be cited for example that the 2- hydroxyethyl second of Maruzen Petrochemical Co., Ltd. Alkene ether (HEVE), diethylene glycol monovinyl base ether (DEGV), 2- hydroxybutyl vinyl ether (HBVE), glycol divinyl Base ether etc..

In addition, the light as the alkali developable that hardening resin composition of the invention can develop in aqueous alkali Solder resist is in use, it is also preferred that using carboxy resin is contained.

(containing carboxy resin)

As carboxy resin is contained, it can be used and contain carboxyl with 1 or more the photosensitive of photosensitive unsaturated double-bond Resin and without photosensitive unsaturated double-bond any one of containing carboxy resin, be not particularly limited.As containing carboxylic Base resin, can be particularly preferably using the resin being exemplified below.

(1) contain carboxy resin as obtained from the copolymerization of unsaturated carboxylic acid and compound with unsaturated double-bond, and Be modified and adjust molecular weight, acid value containing carboxy resin.

(2) make containing unsaturated with oxirane ring and olefinic in carboxyl (methyl) acrylic copolymer resin and 1 molecule It is photosensitive obtained from the compound reaction of group to contain carboxy resin.

(3) make compound and with unsaturated double-bondization that 1 epoxy group and unsaturated double-bond are respectively provided in 1 molecule The copolymer for closing object is reacted with unsaturated monocarboxylic, keeps the secondary hydroxyl generated by the reaction and saturation or unsaturated multi-anhydride anti- It is photosensitive obtained from answering to contain carboxy resin.

(4) after reacting hydroxyl polymer-containing with saturation or unsaturated multi-anhydride, make the carboxylic acid generated by the reaction and 1 Photosensitive hydroxyl obtained from the compound reaction of 1 epoxy group and unsaturated double-bond and carboxyl are respectively provided in molecule Resin.

(5) it reacts multi-functional epoxy compound with unsaturated monocarboxylic, makes one of the secondary hydroxyl generated by the reaction It is photosensitive containing carboxy resin obtained from dividing or all being reacted with multi-anhydride.

(6) make to have in multi-functional epoxy compound and 1 molecule 2 or more hydroxyls and with other than the hydroxyl of epoxy reaction The compound of 1 reactive group reacted with the monocarboxylic acid containing unsaturated group, keep resulting reaction product and multi-anhydride anti- Photoresist containing carboxyl obtained from answering.

(7) make the reaction product of the resin with phenolic hydroxyl group and alkylene oxide or cyclic carbonate with containing unsaturated group Monocarboxylic acid reaction, photoresist containing carboxyl obtained from reacting resulting reaction product with multi-anhydride.

(8) make the chemical combination in multi-functional epoxy compound and 1 molecule at least one alcohol hydroxyl group and 1 phenolic hydroxyl group Object is reacted with the monocarboxylic acid containing unsaturated group, make the alcohol hydroxyl group of resulting reaction product reacted with the anhydride group of multi-anhydride and Obtained photoresist containing carboxyl.

[filler]

In hardening resin composition of the invention, preferably and then contain the filler other than fine powder.It, can as filler With enumerate barium sulfate, barium titanate, amorphous silica, crystallinity silica, fused silica, spherical silicon dioxide, Talcum, clay, magnesium carbonate, calcium carbonate, aluminium oxide, aluminium hydroxide, silicon nitride, aluminium nitride etc..In these fillers, small from specific gravity, In composition can be compounded at high proportion, the aspect that low heat expansion is excellent set out, preferably silica, particularly preferably spherical two Silica.The average grain diameter of filler is preferably 3 μm or less, more preferably 1 μm or less.It should be noted that the average grain of filler Diameter can be found out by laser diffraction formula particle size distribution analyzer.

The compounding amount of filler is 1~90 mass % in the total amount for eliminating solvent, is preferably 2~80 mass %, is more excellent It is selected as 5~75 mass %.Solidfied material by the way that the compounding amount of filler to be set as in above range, after capable of ensuring to solidify well Film performance.

In hardening resin composition of the invention, according to its purposes, and then it can suitably be compounded other usual compoundings Ingredient.As other usual compounding ingredients, for example, curing catalysts, Photoepolymerizationinitiater initiater, colorant, You Jirong Agent etc..

As curing catalysts, phenolic compounds can be enumerated；Imidazoles, 2-methylimidazole, 2- ethyl imidazol(e), 2- ethyl -4- Methylimidazole, 2- phenylimidazole, 4- phenylimidazole, 1- cyano ethyl -2- phenylimidazole, 1- (2- cyano ethyl) -2- ethyl -4- The imdazole derivatives such as methylimidazole；Dicyandiamide, benzyldimethylamine, 2,4,4- (dimethylamino)-N, N- dimethyl benzyl amine, 4- first Amine compounds, adipic dihydrazide, the decanedioic acid two such as oxygroup-N, N- dimethyl benzyl amine, 4- methyl-N, N- dimethyl benzyl amine The hydrazine compounds such as hydrazides；Phosphorus compounds such as triphenylphosphine etc..In addition, as commercially available product, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (Shikoku Chem's system), U-CAT3503N, U-CAT3502T, DBU, DBN, U- CATSA102, U-CAT5002 (San Apro Co. Ltd. system) etc., are used alone or as a mixture two or more.In addition, same Guanamines, acetylguanamine, benzoguanamine, melamine, 2,4- diamino -6- methacryloxyethyl-also can be used in ground S-triazine, 2- vinyl -2,4- diamino-s-triazine, 2- vinyl -4,6- diamino-s-triazine isocyanuric acid adduct, The Striazine derivatives such as 2,4- diamino -6- methacryloxyethyl-s-triazine isocyanuric acid adduct.

In the present invention, phenolic compounds is particularly preferably used.As phenolic compounds, such as 2 kinds can be used alone or in combination Above phenol resol resins, alkylphenol novolac resin, the novolac resin containing triazine structure, bisphenol-A phenol Novolac resin, dicyclopentadiene type phenol resin, Xylock type phenolic resin, Copna resin, terpene modified phenolic resin, Usual substance known in the phenolic compounds such as polyvinylphenols, naphthalene system curing agent, fluorenes system curing agent etc..It is closed as above-mentioned phenolate Object, can enumerate HE-610C, 620C of Air Water Co. Ltd. system, the TD-2131, TD-2106 of Dainippon Ink Chemicals, TD-2093、TD-2091、TD-2090、VH-4150、VH-4170、KH-6021、KA-1160、KA-1163、KA-1165、TD- 2093-60M、TD-2090-60M、LF-6161、LF-4871、LA-7052、LA-7054、LA-7751、LA-1356、LA-3018- 50P, EXB-9854, the SN-170, SN180 of Nippon Steel & Sumitomo Metal Corporation, SN190, SN475, SN485, SN495, SN375, SN395, JX days mine days stone energy Co. Ltd. system DPP, it is bright and chemical conversion Co. Ltd. system HF-1M, HF-3M, HF- 4M、H-4、DL-92、MEH-7500、MEH-7600-4H、MEH-7800、MEH-7851、MEH-7851-4H、MEH-8000H、 MEH-8005, XL, XLC, RN, RS, RX of Mitsui Chemicals, Inc etc., but it is not limited to these.These phenolic compounds can Two or more is used alone or in combination.

The compounding amount of curing catalysts used in the present invention is enough with usually used ratio, relative to Thermocurable tree 100 mass parts of rouge, such as be 1~150 mass parts, preferably 5~100 mass parts, more preferably 10 in the case where phenolic compounds ~50 mass parts are 0.01~10 mass parts, preferably 0.05~5 mass parts, more preferably in the case where other curing catalysts For 0.1~3 mass parts.

Photoepolymerizationinitiater initiater is used to solidify light-cured resin in curable resin, can draw for optical free radical polymerization Send out agent, or light cationic polymerization initiator.

As optical free radical polymerization initiator, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, The benzoins such as benzoin isopropyl ether and benzoin alkyl ethers；Acetophenone, 2,2- dimethoxy -2- phenyl acetophenone, 2,2- The acetophenones such as diethoxy -2- phenyl acetophenone, 1,1- dichloroacetophenone；2- methyl-1-[4- (methyl mercapto) phenyl]-2- Quinoline base -1- acetone, 2- benzyl -2- dimethylamino -1- (4- morpholino phenyl) -1- butanone, 2- (dimethylamino) -2- [(4- Aminomethyl phenyl) methyl] the amino alkylphenones class such as -1- [4- (4- morpholinyl) phenyl] -1- butanone；2-methylanthraquinone, 2- ethyl The Anthraquinones such as anthraquinone, 2- tert-butyl anthraquinone, 1- chloroanthraquinone；2,4- dimethyl thioxanthone, 2,4- diethyl thioxanthone, 2- diuril ton The thioxanthene ketone class such as ketone, 2,4- diisopropylthioxanthone；The ketals class such as acetophenone dimethyl ketal, benzil dimethyl ketal；Two The benzophenones such as Benzophenone；Or xanthene ketone；(2,6- Dimethoxybenzoyl) -2,4,4- amyl phosphine oxide, it is bis- (2,4, 6- trimethylbenzoyl)-phenyl phosphine oxide, 2,4,6- trimethyl benzoyl diphenyl base phosphine oxide, ethyl -2,4,6- front three The phosphinoxides such as base benzoylphenyl phosphinate；Various peroxides, luxuriant titanium series initiators etc..They can be with N, N- Dimethyl amino benzoate, N, N- dimethylaminobenzoic acid isopentyl ester, 4- dimethylaminobenzoic acid pentyl ester, triethyl group Photosensitizer as the tertiary amines such as amine, triethanolamine etc. is applied in combination.

As light cationic polymerization initiator, for example, diazonium salt, salt compounded of iodine, bromide, villaumite, sulfonium salt, The salt such as selenium salt, pyralium salt, thiapyran salt, pyridiniujm；The halogenations chemical combination such as three (trihalomethyl)-s-triazine and its derivative Object；The 2- nitrobenzyl ester of sulfonic acid；Imines disulfonate；Two azo naphthoquinones -4- sulfonate derivatives of 1- oxo -2-；N- hydroxyl Acid imide=sulphonic acid ester；Three (methanesulfonyloxy group) benzene derivatives；Double two azomethane classes of sulfonyl；Sulfonyl carbonyl alkane Class；Two azomethane class of sulfonyl carbonyl；Two sulphones etc..

These Photoepolymerizationinitiater initiaters can be used alone or two or more is applied in combination.

The compounding amount of Photoepolymerizationinitiater initiater is in terms of solid component conversion, relative to 100 mass parts of light-cured resin, such as For 0.05~10 mass parts, preferably 0.1~8 mass parts, more preferably 0.3~6 mass parts.By poly- with light mixing in the range Initiator is closed, the photo-curable on copper becomes sufficiently, and the curability of film is good, and the coating characteristics such as chemical resistance improve, separately Outside, deep curability also improves.

As colorant, the usual well known colorant such as red, blue, green, yellow can be used, can be pigment, dyestuff, pigment Any one of.But it from the viewpoint of reduction carrying capacity of environment and to the influence of human body, is preferably halogen-free.

Blue colorant:

As blue colorant, there are phthalocyanine system, anthraquinone system, pigment system can enumerate the change for being classified as pigment (Pigment) Object is closed, specifically, can enumerate following like that with color index (C.I.；Dyeing and dyer Association of Engineers (The Society of Dyers and Colourists) distribution) number compound: Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 60.

As dyestuff system, can be used Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70、Solvent Blue 83、Solvent Blue 87、Solvent Blue 94、Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc..It is above-mentioned with The substituted or unsubstituted phthalocyanine compound of metal also can be used outside.

Green colourant:

As green colourant, similarly there are phthalocyanine system, anthraquinone system, specifically, Pigment Green can be used 7、Pigment Green 36、Solvent Green 3、Solvent Green 5、Solvent Green20、Solvent Green 28 etc..Also the substituted or unsubstituted phthalocyanine compound of metal can be used other than above-mentioned.

Yellow colorants:

As yellow colorants, there are monoazo system, diazonium system, condensation azo system, benzimidazolone system, isoindolinone System, anthraquinone system etc., can specifically enumerate following colorant.

Anthraquinone system: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193、Pigment Yellow 147、Pigment Yellow 199、Pigment Yellow 202。

Isoindolinone system: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139、Pigment Yellow 179、Pigment Yellow 185。

Be condensed azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128、Pigment Yellow 155、Pigment Yellow 166、Pigment Yellow 180。

Benzimidazolone system: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154、Pigment Yellow 156、Pigment Yellow 175、Pigment Yellow 181。

Monoazo system: Pigment Yellow 1,2,3,4,5,6,9,10,12,61,62,62:1,65,73,74,75, 97、100、104、105、111、116、167、168、169、182、183。

Diazonium system: Pigment Yellow 12,13,14,16,17,55,63,81,83,87,126,127,152,170, 172、174、176、188、198。

Red stain:

As red stain, there is monoazo system, diazonium system, azo lake system, benzimidazolone system, is, diketone pyrrole Simultaneously azole series, condensation azo system, anthraquinone system, quinacridone etc. are coughed up, following substance can be specifically enumerated.

Monoazo system: Pigment Red 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32, 112、114、146、147、151、170、184、187、188、193、210、245、253、258、266、267、268、269。

Diazonium system: Pigment Red 37,38,41.

Monoazo color lake system: Pigment Red 48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,52: 2,53:1,53:2,57:1,58:4,63:1,63:2,64:1,68.

Benzimidazolone system: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185、Pigment Red 208。

System: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red149, Pigment Red 166、Pigment Red 178、Pigment Red 179、Pigment Red 190、Pigment Red 194、Pigment Red 224。

Diketopyrrolo-pyrrole system: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270、Pigment Red 272。

It is condensed azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214、Pigment Red 220、Pigment Red 221、Pigment Red 242。

Anthraquinone system: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149、Solvent Red 150、Solvent Red 52、Solvent Red 207。

Quinacridone: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207、Pigment Red 209。

In addition, the colorants such as purple, orange, dark brown, black can be added for the purpose of adjustment tone.

Specifically, having Pigment Violet 19,23,29,32,36,38,42, Solvent if illustrating Violet 13,36, C.I. pigment orange 1, C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 16, C.I. pigment orange 17, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 51, C.I. pigment orange 61, C.I. pigment Orange 63, C.I. pigment orange 64, C.I. pigment orange 71, C.I. pigment orange 73, C.I. pigment brown 23, C.I. pigment brown 25, C.I. face Expect black 1, C.I. pigment black 7 etc..

The specific compounding ratio of colorant can be suitable according to the type of type, other additives of the colorant used etc. Work as adjustment.

As organic solvent, the ketones such as methyl ethyl ketone, cyclohexanone can be enumerated；The virtues such as toluene, dimethylbenzene, durol Fragrant race's hydro carbons；Methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl The glycol ethers such as ether, diethylene glycol monoethyl ether, dihydroxypropane single-ethyl ether, triethylene glycol monoethyl ether；Ethyl acetate, acetic acid The esters such as carboxylate of butyl ester, cellosolve acetate, diethylene glycol monoethyl ether acetic acid esters and above-mentioned glycol ethers；Ethyl alcohol, third The alcohols such as alcohol, ethylene glycol, propylene glycol；The aliphatic hydrocarbons such as octane, decane；Petroleum ether, naphtha, non-hydrogenated petroleum brain, solvent stone Petroleum series solvent such as cerebrol etc..

In addition, as needed, defoaming agent levelling agent, thixotropy conferring agents thickener, coupling agent, dispersion can be contained Usual additive known in agent, fire retardant etc..

Hardening resin composition of the invention, which can carry out dry film, to be come using can also use in fluid form. In addition, hardening resin composition of the invention, which can also be used as, to be made its coating or even is infiltrated in glass cloth, glass and aromatics to gather The sheet-like fibers matter substrate such as non-woven fabrics of amide carry out semi-solid preparation, prepreg come using.It in fluid form in use, can be with For 1 fluidity, or more than 2 fluidities.As 2 fluidity compositions, such as it can be made and be divided into following composition: fine fibre Cellulose fiber；With in the group being made of the cyclic ether compound with naphthalene skeleton and the cyclic ether compound with anthracene skeleton It is at least one kind of, selected from by the cyclic ether compound with bicyclopentadiene skeleton and with the phenolic aldehyde tree of bicyclopentadiene skeleton At least one kind of, phenoxy resin in the group of rouge composition or selected from by the cyclic ether compound with biphenyl backbone and there is connection It is at least one kind of in the group of the phenolic resin composition of benzene skeleton.

Dry film of the invention has by making hardening resin composition of the invention be coated on carrier thin film and dry Obtained from resin layer.When forming dry film, firstly, by hardening resin composition of the invention with above-mentioned organic solvent diluting And be adjusted to after viscosity appropriate, utilize comma coater, knife type coater, lip type coating machine, bar coating machine, extrusion coated Machine, reverse coating machine, transfer roll-coater, gravure coater, Bracewell coater etc. are on carrier thin film with the painting of uniform thickness Cloth.Later, by the composition after coating usually 40~130 DEG C at a temperature of it is 1~30 minute dry, it is possible thereby to form resin Layer.Coating film thickness is not particularly limited, in general, with the film thickness gauge after drying, at 3~150 μm, preferably in 5~60 μm of model Enclose appropriate selection.

As carrier thin film, plastic film can be used, polyethylene terephthalate (PET) etc. can be used for example Polyester film, Kapton, polyamidoimide film, polypropylene film, polystyrene film etc..To carrier thin film Thickness is not particularly limited, and usually suitably selects in the range of 10~150 μm.More preferably 15~130 μm of range.

After forming the resin layer formed by hardening resin composition of the invention on carrier thin film, for preventing dust It is attached to the purpose on the surface of resin layer, strippable covering film preferably and then on the surface of resin layer is laminated.As peelable From covering film, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface treated paper can be used for example Deng.As covering film, when removing covers film, as long as the bonding force between resin layer is less than resin layer and carrier thin film Bonding force.

It should be noted that in the present invention, it can be by being coated with curable resin of the invention on above-mentioned covering film Composition and drying are to form resin layer, in its surface stacking carrier thin film.That is, when manufacturing dry film in the present invention, as painting Any one of carrier thin film and covering film can be used in the film of cloth hardening resin composition of the invention.

Solidfied material of the invention can be the dry film by the hardening resin composition of aforementioned present invention or aforementioned present invention In resin layer solidification made of.

Electronic component of the invention has the solidfied material of aforementioned present invention, specifically, printed circuit board etc. can be enumerated. Solidfied material of the invention can be suitable in the electronic component for requiring the insulating reliability of interlayer.Particularly, made by being made The hardening resin composition of aforementioned present invention is used to can have good as the multilayer board of interlayer dielectic The insulating reliability of interlayer.

Fig. 2-1 (Fig. 3-1, Fig. 4-1, Fig. 5-1) illustrates that the multilayer printed circuit of an example of electronic component of the invention The partial section view of one configuration example of plate.The multilayer board of diagram can for example manufacture as follows.Firstly, being led being formed with Through hole is formed on the core substrate 2 of body pattern 1.It is appropriate that the formation of through hole can use drill, die punching machine, laser etc. Means carry out.Later, it is roughened using coarse agent.In general, roughening treatment is with N- methyl -2- pyrrole Alkaline aqueous solutions such as the organic solvents such as pyrrolidone, N,N-dimethylformamide, methoxypropanol or caustic soda, caustic potash etc. make It is swollen, and is carried out using oxidants such as bichromate, permanganate, ozone, hydrogen peroxide/sulfuric acid, nitric acid.

Then, conductive pattern 3 is formed by chemical plating, combination of electrolysis plating etc..The work of conductor layer is formed by chemical plating Sequence is after being impregnated in the absorption for carrying out catalyst in the aqueous solution comprising plating catalyst, to be impregnated in plating liquid and coating is precipitated Process.(Subtractive, semi-additive process etc.) according to conventional methods, the conductor layer on the surface of core substrate 2 forms defined circuit Pattern forms conductive pattern 3 in two sides as shown in the drawing.At this point, coating layer is also formed in through hole, as a result, above-mentioned more It is electrically connected, is consequently formed logical between the interconnecting piece 4 of the conductive pattern 3 of layer printed circuit board and the interconnecting piece 1a of conductive pattern 1 Hole 5.

Then, the method appropriate such as silk screen print method, spray coating method, curtain coating processes, such as coating Thermocurable group are utilized After conjunction object and it is made to be heating and curing, forms interlayer insulating film 6.When using dry film or prepreg, carrying out lamination or hot plate pressurization makes It is heating and curing, and forms interlayer insulating film 6.Then such as being formed using means appropriate laser light for by each conductor layer Interconnecting piece between the via hole 7 that is electrically connected, form conductive pattern 8 with method same as above-mentioned conductive pattern 3.In turn, with same The method of sample forms interlayer insulating film 9, via hole 10 and conductive pattern 11.Later, by forming solder mask 12, system in outermost layer Make multilayer board.Among the above, it is said for the example for forming interlayer insulating film and conductor layer on multilayer board It is bright, single substrate also can be used or two sides substrate replaces multilayer board.

<<second embodiment of the present invention>>

The hardening resin composition of second embodiment of the present invention is characterized in that, includes: (A) is at least one-dimensional to be less than The fine powder of 100nm and (B) Thermocurable ingredient.

It is constituted according to the characteristic of this second embodiment of the present invention, the following distinctive effect of the present invention can be played Fruit: in the printed circuit board at least one of recess portion and through hole, even if component installation when high-temperature heating in The wiring of recess portions, the conductor pad on through hole, the via holes such as via hole, the through-hole of the filling of resin filler etc. will not occur Expansion.

About the expansion of the wiring in the high-temperature heating, detailed mechanism is still not clear, it is believed that the reason is that formed by copper Via hole, the difference of the thermal expansion coefficient of through-hole and resin filler at high temperature are big.

Usually, in order to make the organic matter as resin become smaller to the thermal expansion coefficient close to metal, it is known that compounding The method of a large amount of inorganic filler.According to this method, the thermal expansion coefficient near room temperature can be made close to metal really, still, In the high-temperature heating as component installation, even if containing a large amount of filler, thermal expansion coefficient still can be more much larger than metal. Result, it is believed that resin filler can for example be expanded in high-temperature heating in the upper and lower of through hole.In addition, inhibiting the logical of expansion Due to applying pressure the reduction of the reliabilities such as broken string can occur for the wall surface in hole, the bottom of via hole.

This point is to think, according to the present invention, as making fine powder as fine cellulose fiber be scattered in resin In filler, therefore fine powder can obtain such interaction of attracting each other each other, thus show reinforcing effect, even if Also the rising that can inhibit thermal expansion coefficient when high-temperature heating, it is swollen as a result, it is possible to obtain to occur the wiring under high-temperature heating Swollen effect distinctive in this way.

In addition, constituted according to the characteristic of this second embodiment of the present invention, with recess portion and through hole extremely In the manufacturing method of the printed circuit board of few one, when being filled in the solidification of hardening resin composition of recess portion, through hole, The thin resin combination that filler ingredient can be played will not ooze out the distinctive effect of the present invention in this way.

The exudation of the thin resin component of filler ingredient when about the solidification, detailed mechanism is still not clear, but recognizes To be due to that the substance of liquid must be used as resin component in order to adjust viscosity.It is recessed to be filled in via hole, through-hole etc. Portion, through hole resin filler expectation as far as possible without using for volatile ingredient solvent, using this liquid resin component when, In order to solidify it and viscosity can decline when heating, before being cured reaction, because capillarity resin component can be along copper foil Profile exudation.

This point is to think, second embodiment according to the present invention, makes fine powder as fine cellulose fiber It is scattered in resin filler, therefore, because the above-mentioned mutual interaction of aforementioned fine powder can show reinforcing effect, and even if It is also able to maintain viscosity when standing through being heated at high temperature, therefore resin component can be obtained and solidified in advance in this way before copper foil exudation Distinctive effect.

In addition, being constituted according to this characteristic of the invention, in the printing electricity at least one of recess portion and through hole In the plate of road, in the grinding process being filled in after the solidification of hardening resin composition of recess portion, through hole, can play will not Generate the recess distinctive effect of the present invention in this way of hole portion caused by the excessive grinding for smoothing etc..

About the recess of recess portion, through hole in the grinding process, detailed mechanism is still not clear, but resin filler is Come in a manner of being filled up completely in the recess portions such as via hole, through-hole, through hole using, thus, for example with also on through hole periphery and The mode of through hole top exudation fills (Fig. 7-4 (a)), after making its heat cure, by unnecessary part to grind in grinding process Grinding roller etc. is pruned.However, this resin filler for having carried out heat cure can deform if applying pressure, therefore it is easy to produce and cuts Cut remaining (Fig. 7-4 (b)).At this point, residually ground if the condition of grinding is made more strictly not generate cutting, by Recess (Fig. 7-4 (c)) can be generated in exceedingly cutting resin filler, therefore in perforation hole portion.

This point is to think, second embodiment according to the present invention, fine as fine cellulose fiber as making Powder is scattered in resin filler, therefore since the mutual interaction of above-mentioned fine powder can show reinforcing effect, resin Intensity increases, therefore can obtain pressurizing and deformation and become smaller, can equably grind effect distinctive in this way.

Hereinafter, the embodiment for second embodiment of the present invention is described in detail.

[(A) fine powder]

As fine powder used in second embodiment of the present invention, it can be used and illustrate with first embodiment The same substance of substance.By using this fine powder, the hardening resin composition comprising the fine powder is used When resin filler as fillings such as hole portions, fine powder can be obtained and attract such interaction each other, thus Reinforcing effect is showed, so that as described above, the exudation of expansion, resin component after being not likely to produce high-temperature heating, can be formed in The solidfied material for being filled in the recess of filler of hole portion etc. is not easy to produce in grinding process.In addition, the effect is in fine powder In hydrophilic substance show also significantly.

[(B) Thermocurable ingredient]

Thermocurable ingredient is not particularly limited, with the compound of 2 or more cyclic ethers in preferably 1 molecule.The ring-type Ether can be cyclic thioether.Cyclic ether compound can be used singly or in combination of two or more.This cyclic ether In compound, preferred epoxy, oxetane resin, particularly preferred epoxy resin.

As aforementioned epoxy resins, well known epoxy resin can be used.For example, as heat-curing resin, as long as Solidify and show the resin of electrical insulating property by heating, for example, bisphenol A type epoxy resin, Bisphenol F type ring Oxygen resin, bisphenol-s epoxy resin, bisphenol E-type epoxy resin, bis-phenol M type epoxy resin, bis-phenol p-type epoxy resin, bisphenol Z The bisphenol-type epoxy resins such as type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, phenol novolak type epoxy resin, first The phenolic resin varnish type epoxy resins such as phenol phenolic resin varnish, biphenyl type epoxy resin, naphthalene type epoxy resin, anthracene type asphalt mixtures modified by epoxy resin Rouge, biphenyl aralkyl-type epoxy resin, aryl alkene type epoxy resin, four hydroxy phenyl ethane type epoxy resin, phenoxy group type Epoxy resin, dicyclopentadiene-type epoxy resin, norbornene-type epoxy resin, adamantane type epoxy resin, fluorenes type asphalt mixtures modified by epoxy resin Rouge, glycidyl methacrylate copolymerization are epoxy resin, N-cyclohexylmaleimide and glycidyl methacrylate Copolymerization epoxy resin, epoxy-modified polybutadiene rubber derivative, CTBN modified epoxy, trimethylolpropane bunching Water glycerin ether, phenyl -1,3- diglycidyl ether, biphenyl -4,4 '-diglycidyl ether, 1,6 hexanediol diglycidylether, Ethylene glycol or the diglycidyl ether of propylene glycol, d-sorbite polyglycidyl ether, three (2,3- glycidyl) isocyanuric acid esters, Three (2- hydroxyethyl) triglycidyl isocyanurates etc..

For hardening resin composition of the invention, as epoxy resin, by mixing using amine as the ring of precursor Oxygen resin, so as to improve the dispersibility of the fine powder as fine cellulose fiber.Specifically, fine manufacturing When the dispersion of powder, mobility can rise, can lowering viscousity, therefore, workability improve and composition viscosity also under Drop, therefore easily fine powder can be mixed or is compounded with solvent-free.

For four glycidyl group diaminodiphenyl-methane, two can be enumerated using amine as the epoxy resin of precursor The glycidyl compound of toluenediamine, triglycidyl group amino-phenol, the respective positions of glycidyl aniline are different Structure body, with alkyl, the substituent of halogen.As the commercially available product of four glycidyl group diaminodiphenyl-methane, such as can lift Out Sumiepoxy ELM434, (Sumitomo Chemical Co's system), Araldite MY720, MY721, MY9512, MY9612, MY9634, MY9663 (Huntsman Advanced Materials corporation), JER604 (Mitsubishi chemical Co., Ltd's system). As the commercially available product of triglycidyl group amino-phenol, for example, JER630 (Mitsubishi chemical Co., Ltd's system), Araldite MY0500, MY0510 (Huntsman Advanced Materials corporation), ELM100 (Sumitomo Chemical strain formula Commercial firm's system).As the commercially available product of glycidyl phenyl amines, for example, GAN, GOT (Nippon Kayaku K. K's system).

In addition, as hardening resin composition of the invention, if mixing or compounding are as fine cellulose fiber Fine powder and low viscosity is made, then the reduction of heat resistance can be observed, in order to improve the phenomenon, if compounding improves heat resistance Ingredient can then generate the tendency of high viscosity, be matched by the way that bisphenol A type epoxy resin and bisphenol f type epoxy resin is applied in combination It is mixed, then it can eliminate described problem.

In addition, such as alkyl glycidyl ether as 1,6- hexanediol diglycidyl ether since viscosity is low, in group When the viscosity of conjunction object is high, it is expected that being used as diluent, viscosity adjustment.

In the present invention, as (B) Thermocurable ingredient, according to expectation, other other than cyclic ether compound can be used Heat-curing resin.As the heat-curing resin other than cyclic ether compound, as long as being by heating cured resin Can, for example, the novolaks such as phenol resol resins, cresol novolac resin, bisphenol A novolac resin Type phenolic resin, unmodified resol, the modified first of oil being modified with tung oil, linseed oil, walnut oil etc. The phenolic resin such as the resol type phenol resins such as rank phenolic resin, phenoxy resin, urea (urea) resin, melamine resin etc. contain The resin of triazine ring, unsaturated polyester resin, bimaleimide resin, diallyl phthalate resin, organosilicon tree Rouge, the resin with benzoxazine ring, norbornene resin, cyanate ester resin, isocyanate resin, carbamate tree Rouge, benzocyclobutane olefine resin, maleimide resin, bismaleimide-triazine resin, poly methylene imine resin, Thermocurable are poly- Acid imide, bicyclopentadiene biphenol ester compounds, bisphenol-A diacetate esters, diphenyl phthalate, terephthalic acid (TPA) hexichol Bis- [4- (methoxycarbonyl) phenyl ester] isoreactivity ester compounds of ester, terephthalic acid (TPA) etc..

(B) compounding amount of Thermocurable ingredient is preferably 10~70 mass % relative to the total amount of composition.For 10 matter When measuring % or more, the workability such as printing are excellent.When for 70 mass % or less, thermal expansion becomes lower.More preferably 20~60 matter Measure %.

[curing agent]

It is preferable to use curing agent according to expectation for hardening resin composition of the invention.

As curing agent of the invention, imidazolium compounds can be used for example.As imidazolium compounds, for example, 2-methylimidazole, 4- methyl -2- ethyl imidazol(e), 2- phenylimidazole, 4- methyl -2- phenylimidazole, 1 benzyl 2 methyl imidazole, 2- ethyl imidazol(e), 2 isopropyl imidazole, 1- cyano ethyl -2-methylimidazole, 1- cyano ethyl -2-ethyl-4-methylimidazole, 1- The imdazole derivatives such as cyano ethyl -2- undecyl imidazole.

In addition, the imidazolium compounds comprising triazine structure can also be enumerated as imidazolium compounds.As including triazine knot The imidazolium compounds of structure can enumerate 2,4- diamino -6- [2 '-methylimidazolyls-(1 ')]-ethyl-s-triazine, 2,4- diamino Base -6- [2 '-methylimidazolyls-(1 ')]-ethyl-s-triazine, 2,4- diamino -6- [2 '-undecyl imidazole base-(1 ')] - Ethyl-s-triazine, 2,4- diamino -6- [2 '-ethyls -4 '-methylimidazolyl-(1 ')]-ethyl-s-triazine etc..As them Commercially available product example, 2MZ-A, 2MZ-AP, 2MZA-PW, C11Z-A, 2E4MZ-A (four countries' chemical conversion industry strain formula meeting can be enumerated Society's system) etc..

In imidazolium compounds, preferably 2,4- diamino -6- [2 '-methylimidazolyls-(1 ')]-ethyl-s-triazine, 2,4- bis- Amino -6- [2 '-ethyls -4 '-methylimidazolyl-(1 ')]-ethyl-s-triazine.The preservation of hardening resin composition is steady as a result, It is qualitative excellent, the solidfied material that will not be cracked because the short time solidifies can be obtained.

As curing agent, the compound other than imidazolium compounds can be used, dicyandiamide can be used for example and derive with it Object, melamine and its derivative, diaminomaleonitrile and its derivative, diethylenetriamines, trien, four methylenes Five amine of base, bis- (hexa-methylene) triamines, triethanolamine, diaminodiphenyl-methane, benzyldimethylamine, 2,4,4- (dimethylamino Base)-N, N- dimethyl benzyl amine, 4- methoxyl group-N, N- dimethyl benzyl amine, 4- methyl-N, N- dimethyl benzyl amine, adipic acid The amines such as the organic acids hydrazides such as two hydrazides, sebacic dihydrazide, 1,8- diazabicyclo [5.4.0] endecatylene -7,3,9- are bis- Four oxaspiro [5.5] hendecane of (3- aminopropyl) -2,4,8,10- or triphenylphosphine, tricyclohexyl phosphine, tributylphosphine, methyl The organic phosphine compounds such as diphenylphosphine, phenolic compounds etc..In addition, as commercially available product, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (Shikoku Chem's system), ATU (Ajincomoto Co., Inc's system), U-CAT3503N, U-CAT3502T, DBU, DBN, U-CATSA102, U-CAT5002 (San Apro Co. Ltd. system) etc..Known dicyandiamide, trimerization Bis- [2- (3,5- diamino -2,4,6- triazine base) the ethyl] -2,4,8,10- of cyanamide, acetylguanamine, benzoguanamine, 3,9- Guanamines and its derivatives and their acylate, epoxy adduct etc. such as four oxaspiros [5.5] hendecane have close with copper Conjunction property, rust-preventing characteristic, the curing agent for serving not only as epoxy resin works, and can also assist in the copper for preventing printed circuit board Discoloration.

As above-mentioned phenolic compounds, such as it can come alone or in combination of two kinds or more using following substances: phenol novolacs Resin, alkylphenol novolac resin, the novolac resin containing triazine structure, bisphenol A novolac resin, two rings penta 2 The phenolate such as ene-type phenolic resin, Xylock type phenolic resin, Copna resin, terpene modified phenolic resin, polyvinylphenols are closed Usual substance known in object, naphthalene system curing agent, fluorenes system curing agent etc..As above-mentioned phenolic compounds, Water plants of Air can be enumerated HE-610C, 620C of formula commercial firm, Dainippon Ink Chemicals TD-2131, TD-2106, TD-2093, TD-2091, TD- 2090、VH-4150、VH-4170、KH-6021、KA-1160、KA-1163、KA-1165、TD-2093-60M、TD-2090-60M、 LF-6161, LF-4871, LA-7052, LA-7054, LA-7751, LA-1356, LA-3018-50P, EXB-9854, Nippon Steel live SN-170, SN180, SN190, SN475, SN485, SN495, SN375, SN395, JX mine day, stone day of aurification Co. Ltd. system The DPP of energy Co. Ltd. system, bright and chemical conversion HF-1M, HF-3M of Co. Ltd. system, HF-4M, H-4, DL-92, MEH-7500, MEH-7600-4H, MEH-7800, MEH-7851, MEH-7851-4H, MEH-8000H, MEH-8005, Mitsui Chemicals, Inc XL, XLC, RN, RS, RX etc. of system, but it is not limited to these.

Curing agent can be used singly or in combination of two or more.The compounding amount of curing agent is relative to thermosetting The property changed ingredient can be known usual compounding amount, such as relative to 100 mass parts of epoxy resin, be preferably set to 0.01~10 matter Measure part.Wherein, when curing agent is phenolic compounds, relative to 100 mass parts of epoxy resin, 1~150 mass parts are preferably set to.

[(C) boric acid ester compound]

Hardening resin composition of the invention can contain boric acid ester compound.Boric acid ester compound, which has, further to be mentioned The effect of the storage stability of high resin composition, it is therefore desirable for using.Think boric acid ester compound by solidifying with potentiality The surface of promotor is reacted, and the surface progress of modification potentiality curing agent is encapsulated, thus plays this effect.As borate Compound, can enumerate trimethylborate, triethyl borate, three n-propyl of boric acid, triisopropyl borate ester, tri-n-butyl borate, Triamylborate, boric acid triallyl, the own ester of boric acid three, tricyclohexyl borate, three monooctyl ester of boric acid, three nonyl ester of boric acid, boric acid three Last of the ten Heavenly stems ester, three (dodecyl) borates, three (cetyl) borates, three (octadecyl) borates, three (2- ethyl hexyl oxygen Base) borine, bis- (tetra- oxaundecyls of 1,4,7,10-) (five oxa- myristyl of 1,4,7,10,13-) (1,4,7- trioxa Undecyl) borine, tribenzyl borate, triphenyl borine acid esters, three-o-tolyl borates, three-tolyl borates, Triethanolamine borate etc..These can be used as reagent and buy.In addition, as commercially available product, can enumerate as epoxy resin with Cureduct L-07N, the L-07E (Shikoku Chem's system) of the compounding product of phenol resol resins.

Boric acid ester compound can be used singly or in combination of two or more.The compounding of boric acid ester compound Amount is preferably set to 0.01~3 mass parts relative to 100 mass parts of Thermocurable ingredient.When to be more than 0.01 mass parts, save steady It is qualitative to become good.For 3 below the mass when, curability becomes good.

[(D) filler]

Hardening resin composition of the invention can be further containing the filler other than aforementioned (A) fine powder.As Filler other than aforementioned (A) fine powder, the requirement characteristic of hardening resin composition according to the present invention, as long as appropriate used Organic filler, inorganic filler then can be used in well known filler, more preferably uses inorganic filler.

As inorganic filler, barium sulfate, barium titanate, amorphous silica, crystallinity silica, melting can be enumerated Silica, spherical silicon dioxide, talcum, clay, magnesium carbonate, calcium carbonate, aluminium oxide, aluminium hydroxide, mica powder, noy fort silicon Soil, silicon nitride, aluminium nitride etc..In inorganic filler, preferred calcium carbonate.

The shape of filler can enumerate spherical, needle-shaped, plate, flakey, hollow form, it is unsetting, hexagonal, cubic, Flake etc., it is preferably spherical from high fillibility aspect.

Filler can be used singly or in combination of two or more.The compounding amount of filler is relative to composition Total amount is preferably 10~70 mass %, more preferably 20~60 mass %.If 10 mass % or more, then the workability of printing etc. It is excellent.If 70 mass % hereinafter, then thermally expanding becomes lower.

[other compositions]

In hardening resin composition of the invention, do not need centainly to use organic solvent, but to adjust composition For the purpose of viscosity etc., organic solvent can be added with the degree for not generating gap.

In turn, in hardening resin composition of the invention, as needed, can be compounded phthalocyanine blue, phthalocyanine green, Usual colorant known in iodine is green, diazonium is yellow, crystal violet, titanium oxide, carbon black, naphthalene are black etc., in order to assign preservation when keeping Stability can be compounded known in hydroquinone, hydroquinone monomethyl ether, tert-butyl catechol, pyrogallol, phenthazine etc. and be used to It is usual thickener known in thermal polymerization inhibitor, clay, kaolin, organobentonite, montmorillonite etc. or thixotropic agent, organic The adaptations such as the defoaming agents such as silicon systems, fluorine system, macromolecular and/or levelling agent, imidazoles system, thiazole system, triazole system, silane coupling agent The known usual additive kind of imparting agent, Photoepolymerizationinitiater initiater, dispersing agent, fire retardant etc.

Hardening resin composition of the invention can be 1 fluidity, or more than 2 fluidities.

The hardening resin composition of the invention obtained as described above can use the method used in the past, such as silk Net print process, roller coating method, mold coating method etc. are easily filled in the hole portions such as via hole, the through-hole of printed circuit board.

Therefore, the viscosity of hardening resin composition of the invention is preferably 100~1000dPas's at 25 ± 1 DEG C Range, further preferably 200~900dPas, particularly preferably 300~800dPas.By being set as this range, hole The filling in portion is easy, and gap will not be generated etc., it can be filled in recess portion, through hole well.

In addition, the glass transition temperature (Tg) of hardening resin composition of the invention be preferably 150 DEG C or more, it is more excellent It is selected as 160 DEG C or more.When Tg is 150 DEG C or more, it is able to suppress the generation of removing (layering).

Solidfied material of the invention is to solidify the hardening resin composition of the second embodiment of aforementioned present invention 's.

Printed circuit board of the invention is at least one consolidating by second embodiment of the present invention of recess portion and through hole Obtained from the solidfied material filling of the property changed resin combination.

Hereinafter, filling curability tree of the invention in the recess portions such as via hole, through-hole set on wiring plate, through hole Oil/fat composition is formed on pad, wiring, referring to the one of the manufacturing method of Fig. 7-1 printed circuit board for illustrating to be thusly-formed Example.

(1) filling perforation

Firstly, being formed with the circuit board of through-hole 103 and conductor circuit layers 104 as shown in Fig. 7-1 (a), in substrate 102 The through-hole 103 being arranged on 101 is (when using multilayer board as core substrate, other than through-hole and then via hole etc. Recess portion) in, hardening resin composition of the invention is filled as shown in Fig. 7-1 (b).For example, throughhole portions are equipped with opening Exposure mask is placed on substrate, is filled in through-hole using print process or point print process etc..

Herein, it as circuit board 101, can be properly used following circuit board: being laminated with copper foil with drill The resins base such as glass epoxide substrate or polyimide resin substrate, bismaleimide-triazine resin substrate, fluororesin substrate Open through hole on the substrates such as material, ceramic base material, metal base 102, wall surface to through hole and copper foil surface implement chemical plating or And then implement electrolysis plating, form the circuit board of through-hole 103 and conductor circuit layers 104.As plating, plated usually using copper It covers.

(2) it grinds

Then, it heats filled hardening resin composition about 30~90 minutes or so with about 90~130 DEG C, makes it Precuring.The hardness of so solidfied material 105 through precuring is relatively low, therefore can will be seeped from substrate surface by physical grinding Unnecessary part out is readily removable, and flat surface can be made.And then it is secondary with about 140~180 DEG C of about 30~90 points of heating Clock or so carries out formal solidification (completing solidification).

It should be noted that the reactivity that " precuring " or " precuring object " described herein typically refers to epoxy is 80% ~97% state.In addition, the hardness of above-mentioned precuring object can be controlled by changing heating time, the heating temperature of precuring System.Later, as shown in Fig. 7-1 (c), by grinding by the unnecessary part of the formal solidification object 105 oozed out from through-hole remove into Row planarization.Grinding can be carried out by belt sander, polishing grinding etc..

(3) formation of conductor circuit layers

It carries out forming plating film on the surface of the substrate of the filling perforation of through-hole as shown in Fig. 7-1 (d).Later, resist is formed, (not shown) is etched to the non-formation part of resist.Then, by removing resist, as shown in Fig. 7-1 (e), formation is led Body circuit layer 106.

As described above, hardening resin composition of the invention can suitably be used as such setting shown in Fig. 7-1 The resin filler of through-hole on a printed circuit, and then be suitable for use as being arranged as shown in Fig. 7-2, Fig. 7-3 more The resin filler of the through-hole of layer printed circuit board, via hole, but these purposes are not limited to, it can be used for such as sealing material The purposes such as material.

Embodiment

Hereinafter, the present invention is described in more detail using embodiment.

<first embodiment>

[preparation of fibrous fine cellulose powder]

Production Example 1 (CNF1)

By BK bleached kraft pulp fibres (the Fletcher Challenge Canada corporation Machenzie of coniferous tree CSF650ml after) being sufficiently stirred in the ion exchange water of 9900g, TEMPO is successively added relative to pulp quality 100g (ALDRICH corporation 2,2,6,6- tetramethyl piperidine 1- oxygroup free radical) 1.25 mass %, 12.5 mass % of sodium bromide, secondary chlorine Sour 28.4 mass % of sodium.Using pH-stat, 0.5M sodium hydroxide is added dropwise and pH is remained 10.5.Reaction is carried out 120 minutes After (20 DEG C), stop the dropwise addition of sodium hydroxide, obtains oxidation paper pulp.It is using ion exchange water that obtained oxidation paper pulp is sufficiently clear It washes, is then carried out dehydrating.Later, oxidation paper pulp 3.9g and ion exchange water 296.1g is used into high-pressure homogenizer ((Sugino machine corporation, Starburst Lab HJP-25005) carries out miniaturization processing 2 times with 245MPa, obtains The dispersion liquid (1.3 mass % of solid component concentration) of carboxylic fine cellulose powder.

Then, the dispersion liquid 4088.75g of the carboxylic fine cellulose powder of gained is put into beaker, addition ion is handed over The aqueous solution that 0.5 mass % is made in water 4085g is changed, is stirred 30 minutes for (25 DEG C) at room temperature with mechanical agitator.Then, it puts into 1M aqueous hydrochloric acid solution 245g reacts it 1 hour.After reaction, reprecipitation is carried out with acetone, filtered, later, It is cleaned with acetone/ion exchange water, removes demineralizing acid and salt.It is eventually adding acetone to be filtered, obtain carboxylic fine Dispersion liquid (the solid component concentration 5.0 of the acid type cellulose powder containing acetone for the state that cellulose powder is swollen in acetone Quality %).After reaction, it filters, later, is cleaned with ion exchange water, remove demineralizing acid and salt.Solvent is carried out with acetone After displacement, solvent displacement is carried out with DMF, the acid type containing DMF for obtaining the state of carboxylic fine cellulose powder swelling is fine Tie up the dispersion liquid (avarage fiber diameter 3.3nm, 5.0 mass % of solid component concentration) of plain powder.

Production Example 2 (CNF2)

The dispersion liquid 40g and hexyl amine 0.3g of acid type cellulose powder obtained in Production Example 1 containing DMF are put into and are had Magnetic stirring apparatus, stirrer beaker in, made it dissolve with ethyl alcohol 300g.React reaction solution 6 hours under room temperature (25 DEG C). It is filtered after reaction, carries out cleaning with DMF and solvent is replaced, thus obtain amine by ionic bonding and microfibre The dispersion liquid (5.0 mass % of solid component concentration) of the fine cellulose powder of plain powder connection.

The dispersibility of the CNF2 manufactured with the method for the Production Example 2 is especially good, even if special without using high-pressure homogenizer etc. Dispersion machine, can also be dispersed with usual way.

Production Example 3 (CNF3)

By fine cellulose powder ((the Sugino machine corporation BiNFi-s, avarage fiber diameter of threadiness 80nm) 10 mass % dewatering and filtering, is added the carbitol acetate of 10 times of amounts of screening quality, and stirring is filtered after 30 minutes.It will The replacement operator is repeated 3 times, and the carbitol acetate of 20 times of amounts of addition screening quality makes the dispersion of fine cellulose powder Liquid (5.0 mass % of solid component concentration).

[preparation of Cellulose nanocrystal particle]

Production Example 4 (CNC1)

The scraps of paper of coniferous tree bleached kraft pulp after drying are handled with shredding machine and sprayer of hammer crusher, cotton is made The fiber of shape.The fiber of the cotton like is taken out, 100g is calculated as with adiabatic drying quality, is suspended in 64% aqueous sulfuric acid 2L, in 45 DEG C hydrolyze it 45 minutes.

After the filtering of thus obtained suspension, the ion exchange water of 10L is injected, stirring keeps its evenly dispersed, divided Dispersion liquid.Then, it is repeated 3 times the process that dehydration is filtered to the dispersion liquid, obtains dehydration piece.Then, with the ion exchange of 10L Water dilutes obtained dehydration piece, adds the sodium hydrate aqueous solution of 1N bit by bit while stirring, makes pH 12 or so.It Afterwards, by the suspension filtering means dehydration, the ion exchange water of 10L is added, stirring is filtered dehydration, repeats the process 2 times.

Then, ion exchange water is added in obtained dehydration piece, prepares 2% suspension.With wet type micro-granulating device ((Sugino machine corporation " Ultimaizer ") makes the suspension, by 10 times, obtain fiber with the pressure of 245MPa Plain nano-crystalline granule aqueous dispersions.

Later, after carrying out solvent displacement with acetone, solvent displacement is carried out with DMF, obtains Cellulose nanocrystal granules swell The DMF dispersion liquid (5.0 mass % of solid component concentration) of state.By the Cellulose nanocrystal particle AFM in gained dispersion liquid It observes and measures, as a result average crystallite width is 10nm, average crystallite length is 200nm.

Production Example 5 (CNC2)

Other than the cellulosic material of Production Example 4 to be changed to absorbent cotton (white cross corporation), with Same Way come Manufacture, obtains the DMF dispersion liquid (5.0 mass % of solid component concentration) of the state of Cellulose nanocrystal granules swell.By gained Cellulose nanocrystal particle in dispersion liquid is observed and is measured with AFM, and as a result average crystallite width is 7nm, average crystallite length For 150nm.

(embodiment 1-1~1-15, comparative example 1-1~1-8)

According to the record in following table 1~3, after the compounding stirring of each ingredient, the high pressure using the mechanical industrial system of Jitian is equal Change device Nanovater NVL-ES008, being repeated 6 times makes its dispersion, prepares each composition.It should be noted that in table 1~3 Numerical value indicates mass parts.

For each composition obtained in Examples and Comparative Examples, evaluate coefficient of thermal expansion, resistance to soldering heat performance, insulating properties, Toughness (elongation).Evaluation method is as follows described.

[coefficient of thermal expansion]

In 38 μm of thickness of PET film, it is coated with each composition using 120 μm of the applicator in gap, in heated air circulation type It is 10 minutes dry with 90 DEG C in drying oven, obtain the dry film with the resin layer of each composition.Later, existed using vacuum laminator 60 DEG C, under conditions of pressure 0.5MPa in being crimped 60 seconds on 18 μm of thickness of copper foil, be laminated the resin layer of each composition, remove PET film.Then, being heated 30 minutes with heated air circulation type drying oven at 180 DEG C makes its solidification, removes, is obtained by each from copper foil The film sample that the solidfied material of composition is formed.Gained film sample is cut into 3mm wide × 30mm long, coefficient of thermal expansion measurement is made Use test film.For the test film, TA Instrument corporation TMA (Thermomechanical Analysis) is used Q400, to be warming up to 250 DEG C with 5 DEG C/min from 20 DEG C, connect under 16mm, load 30mN, nitrogen atmosphere between stretch mode and chuck , it is cooled to 20 DEG C from 250 DEG C with 5 DEG C/min, measures coefficient of thermal expansion α 1 and α 2 (ppm/K).Together by their measurement result Shown in table 1~3.

[resistance to soldering heat performance]

On the FR-4 copper-clad laminated board of size 150mm × 95mm, 1.6mm thickness, by each composition with 80 mesh Supreme Being's Telons (Tetron) silk-screen printing of bias version carries out whole face coating, 30 minutes dry in 80 DEG C in heated air circulation type drying oven, then, It is heating and curing at 180 DEG C 30 minutes, obtains the test substrate for foring the resin layer of the solidfied material comprising each composition.At this The resin layer surface coating rosin series scaling powder of test substrate uses propylene glycol monomethyl ether solder laminar flow 60 seconds of 260 DEG C Acetic acid esters is then cleaned with ethyl alcohol.For the test substrate after cleaning, visually to observe the expansion, removing, surface shape of resin layer Resistance to soldering heat performance is evaluated in the variation of state.About evaluation criteria, by resin layer observe expansion, removing, by surface dissolution, Abnormal situation caused by softening etc. is set as ×, above-mentioned abnormal situation will be not observed and be set as zero.By its evaluation result one And shown in table 1~3.

[insulating properties]

Each composition is coated on to 38 μm of thickness of PET film with the applicator in 120 μm of gap, it is dry with heated air circulation type Furnace is 10 minutes dry at 90 DEG C, obtains the dry film with the resin layer of each composition.Later, on 1.6mm thickness FR-4 substrate In the A test piece of the IPC MULTI-PURPOSE TEST BOARDB-25 formed with 35 μm of copper thickness, with vacuum laminator 60 DEG C, crimp 60 seconds under conditions of pressure 0.5MPa, be laminated the resin layer of each composition, remove PET film, it is dry with heated air circulation type Dry furnace heats 30 minutes at 180 DEG C makes its solidification.Then, the lower end of IPC MULTI-PURPOSE TEST BOARDB-25 is cut off Portion (is cut off) as electrically independent terminal with the dotted line part of Fig. 1-4.Moreover, the top cathode of A test piece, lower part is made to be anode, Apply the bias of DC500V, measures insulating resistance value, evaluated.

For evaluation criteria, the situation that insulating resistance value is 100G Ω or more is set as zero, insulating resistance value is less than The case where 100G Ω is set as ×.By its evaluation result it is shown in table 1 together~3.

[toughness]

Each composition is coated with the applicator in 200 μm of gap in 38 μm of thickness of PET film, it is dry with heated air circulation type Furnace makes it dry 20 minutes at 90 DEG C, obtains the dry film with the resin layer of each composition.Then, glassy surface court will be made with adhesive tape On 18 μm of thickness of electrolytic copper foil be fixed on the FR-4 copper-clad laminated board of thickness 1.6mm, by aforementioned dry film vacuum lamination Machine crimps 60 seconds under conditions of 60 DEG C, pressure 0.5MPa, and the resin layer of each composition is laminated on aforementioned electrolytic copper foil, is connect , PET film is removed, is heated 30 minutes with heated air circulation type drying oven at 180 DEG C, solidifies resin layer.It then, will be fixed Adhesive tape removing, and then electrolytic copper foil is removed, obtain the film sample comprising resin layer.It then, will be upper according to JIS K7127 It states film sample and is cut into defined size, make evaluation test film.It is small-sized using Shimadzu Seisakusho Ltd.'s system for the test film Desktop tester EZ-SX, with tensile speed 10mm/ points of measurements stress [MPa] and strain [%].Strain [%] at this time is test It is higher can be evaluated as bigger toughness, therefore evaluates toughness by the strain [%] for elongation when piece is broken.

For evaluation criteria, by strain [%] less than 2.0% the case where is set as ×, 2.0% or more situation is set as 〇. By its evaluation result it is shown in table 1 together~3.

[table 1]

* 1-1) 50 mass % of heat-curing resin 1-1:Epiclon HP-4032 Dainippon Ink Chemicals solid component Cyclohexanone varnish (cyclic ether compound with naphthalene skeleton)

* 1-2) heat-curing resin 1-2:NC-7300L Nippon Kayaku K. K solid component 50 mass % hexamethylene Ketone varnish (cyclic ether compound with naphthalene skeleton)

* 1-3) heat-curing resin 1-3:YX-8800 Mitsubishi chemical Co., Ltd solid component 50 mass % hexamethylene Ketone varnish (cyclic ether compound with anthracene skeleton)

* 1-4) heat-curing resin 1-4:Epiclon HP-7200 solid component 50 the cyclohexanone varnish of mass % (have The cyclic ether compound of bicyclopentadiene skeleton)

* 1-5) heat-curing resin 1-5:NC-3000H Nippon Kayaku K. K solid component 50 mass % hexamethylene Ketone varnish (cyclic ether compound with biphenyl backbone)

* 1-6) heat-curing resin 1-6:YX-4000 Mitsubishi chemical Co., Ltd solid component 50 mass % hexamethylene Ketone varnish (cyclic ether compound with biphenyl backbone)

* 1-7) heat-curing resin 1-7:Epiclon N-740 Dainippon Ink Chemicals solid component 50 mass % ring Hexanone varnish

* 1-8) 830 Dainippon Ink Chemicals's system of heat-curing resin 1-8:Epiclon

* 1-9) heat-curing resin 1-9:JER827 Mitsubishi chemical Co., Ltd system

* 1-10) phenoxy resin 1-1:YX6954 Mitsubishi chemical Co., Ltd solid component 30 mass % cyclohexanone Varnish

* 1-11) curing agent 1-1:HF-1 is bright and is melted into 60 mass % cyclohexanone varnish of Co. Ltd. system solid component

* 1-12) curing agent 1-2: bisphenol-A diacetate esters Tokyo Chemical Industry Co., Ltd system (active ester)

* 1-13) curing catalysts 1-1:2E4MZ (2-ethyl-4-methylimidazole) Shikoku Chem system

* 1-14) filler 1-1:Adma Fine SO-C2 Co., Ltd.'s Admatechs system (silica)

* 1-15) organic solvent 1-1: dimethylformamide

* 1-16) defoaming agent 1-1:BYK-352 BYK Chemie JAPAN Co. Ltd. system

[table 2]

* 1-17) filler 1-2:B-30 Sakai Chemical Industry Co., Ltd. Sulphuric acid barium

* 1-18) filler 1-3:DAW-07 Denka Co. Ltd. system aluminium oxide

* 1-19) dispersing agent 1-1:DISPERBYK-111 BYK Chemie corporation

[table 3]

Clearly confirmed by the result recorded in table 1~3, by the way that fine cellulose powder and fine cellulose is applied in combination Filler other than powder can obtain not only low-heat capable of being maintained swollen in room temperature but also the high-temperature area in component installation The solidfied material of each excellent such as swollen rate and toughness.In addition, can confirm embodiment by the evaluation result of resistance to soldering heat performance The heat resistance of each composition, chemical resistance are excellent, and can be used as wiring plate with composition.In turn, it is able to confirm that It is reduced by using active ester as curing agent, relative dielectric constant and dielectric loss angle tangent.

<second embodiment>

As fine cellulose fiber CNF1~CNF3 and Cellulose nanocrystal particle CNC1, CNC2, using with it is first real Apply the same Production Example 1~5 of example.

Synthesis example 1 (varnish 1)

Add in 2 liters of removable flasks for having blender, thermometer, reflux condenser, dropping funel and nitrogen ingress pipe Enter the diethylene glycol dimethyl ether 900g as solvent and the peroxidating 2 ethyl hexanoic acid tert-butyl ester (day as polymerization initiator Oily Co. Ltd. system, trade name；Perbutyl O) 21.4g, it is heated to 90 DEG C.After heating, thereto, by methacrylic acid 309.9g, methyl methacrylate 116.4g and lactone-modified 2-hydroxyethyl methacrylate (Co., Ltd.'s Daicel system, Trade name；Placcel FM1) 109.8g and bis- (4- tert-butylcyclohexyl) peroxy dicarbonates as polymerization initiator (Japan Oil Co's system, trade name；Peroyl TCP) 21.4g mono- reinstate 3 hours be added dropwise.In turn, it is carried out 6 hours it is ripe Change, thus obtains carboxylic copolymer resins.It should be noted that these reactions carry out under nitrogen atmosphere.

Then, methacrylic acid 3,4- epoxy cyclohexyl (Co., Ltd. are added in obtained carboxylic copolymer resins Daicel system, trade name；Cyclomer A200) 363.9g, as the dimethyl benzyl amine 3.6g of ring opening catalyst, as poly- The hydroquinone monomethyl ether 1.80g for closing inhibitor, is heated to 100 DEG C, is stirred to it, and the open loop for thus carrying out epoxy adds At reaction.After 16 hours, obtain the acid value comprising solid component be 108.9mgKOH/g, matter average molecular weight 25,000 containing carboxylic The solution of 53.8 mass % (nonvolatile component) of base resin.

Synthesis example 2 (varnish 2)

The diethyl two as solvent is added in the flask for having thermometer, blender, dropping funel and reflux condenser Alcohol list monoethyl ether acetate and azobis isobutyronitrile as catalyst are heated to 80 DEG C under nitrogen atmosphere, small with about 2 When the monomer for mixing methacrylic acid and methyl methacrylate with the molar ratio of 0.40:0.60 is added dropwise.In turn, it is stirred for After 1 hour, 115 DEG C are raised the temperature to, its inactivation is made to obtain resin solution.

After resin solution cooling, Tetrabutylammonium bromide is used for as catalyst, at 95~105 DEG C, with 30 The condition of hour makes butyl glycidyl ether carry out addition reaction with 0.40 molar ratio and the equivalent of the carboxyl of gained resin, It is cooling.

In turn, for the OH base of resin obtained in above-mentioned, at 95~105 DEG C, with 8 hours conditions, make tetrahydro neighbour's benzene Dicarboxylic acid anhydride carries out addition reaction with 0.26 molar ratio.It is taken out after being cooled to, obtaining the acid value comprising solid component is The solution of 78.1mgKOH/g, the 50 mass % (nonvolatile component) Han carboxy resin that matter average molecular weight is 35,000.

Synthesis example 3 (varnish 3)

In the flask for having thermometer, blender, dropping funel and reflux condenser, cresol novolak type ring is added Oxygen resin (Dainippon Ink Chemicals's system, Epiclon N-680, epoxide equivalent=210) 210g and the carbitol acetic acid as solvent Ester 96.4g makes its heating for dissolving.Then, it is added thereto as the hydroquinone 0.1g of polymerization inhibitor and as catalysts Triphenylphosphine 2.0g.The mixture is heated to 95~105 DEG C, acrylic acid 72g is slowly added dropwise, reacts 16 hours to acid value change At until 3.0mgKOH/g or less.After the reaction product is cooled to 80~90 DEG C, tetrabydrophthalic anhydride 76.1g is added, By infrared spectrum analysis, until the absorption peak (1780cm of acid anhydrides^-1) until disappearance, its is made to react for about 6 times.To the reaction solution The aromatic system solvent Ipuzoru#150 of the middle Idemitsu Kosen Co., Ltd. that 96.4g is added, takes out after dilution.So obtain Carboxylic photosensitive polymer solution nonvolatile component be 65 mass %, the acid value of solid component is 78mgKOH/g.

According to the record in following table 4~12, after the compounding stirring of each ingredient, the high pressure using the mechanical industrial system of Jitian is equal Change device Nanovater NVL-ES008, being repeated 6 times makes its dispersion, prepares each composition.It should be noted that in table 4~12 Numerical value indicates mass parts.

[layer insulation reliability]

(heat-curable composition)

In 38 μm of thickness of PET film, each composition shown in table 4~6, In are coated with 120 μm of the applicator in gap It is 10 minutes dry in 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, in In the A test piece for the IPC MULTI-PURPOSE TEST BOARD B-25 that 1.6mm thickness FR-4 substrate is formed with 35 μm of copper thickness (part shown in the arrow in Fig. 2-2: the right side of the comb pattern of figure lower part), using vacuum laminator with 60 DEG C, pressure The condition of 0.5MPa crimps 60 seconds, is laminated the resin layer of each composition, PET film is removed, with heated air circulation type drying oven in 180 DEG C heating makes its solidification in 30 minutes.Then, according to permanganic acid de-smear (ATOTECH corporation), electroless copper (Thru-Cup PEA, upper industrial group, village system), the sequence of cathode copper plating handled, implement 25 μm of copper thickness of copper plating. Then, make annealing treatment within 60 minutes in 190 DEG C in heated air circulation type drying oven, obtain the test for implementing copper plating Substrate.Then, the acidproof adhesive tape that will be shaped to the circle of diameter 1cm is attached at copper plating in a manner of the center for becoming A test piece and is covered with, The copper plating other than the acidproof tape portion on resin cured matter is utilized into etching with 40 DEG C of 40 mass % ferric chloride in aqueous solution Removal.Test substrate at this time is following state: in the A test piece of IPC MULTI-PURPOSE TEST BOARD B-25, respectively The solidfied material of composition is formed in the form of film, is formed on the state of the circular copper plating of diameter 1cm (referring to figure 2-3).Then, it is covered in the plating of circular copper and electric wire is loaded into wire bonding material and soldering iron, for IPC MULTI-PURPOSE TEST Electric wire is similarly loaded onto the wiring of BOARD, regard circle as anode, is regard wiring as cathode, is applied the voltage of 3.3V, In Test in 200 hours is carried out in the environment of 130 DEG C 85%.Test film makes 10 for each composition.At this point, often measurement is exhausted Edge resistance will become 1 × 10⁶NG is set as at the time of Ω or less.It all will be evaluated as ◎ without NG person until off-test, by 1~4 A NG person is evaluated as zero, and 5~9 NG persons are evaluated as △, will all be evaluated as NG person ×.Show the results of the evaluation table 4 ~6.

(Photosetting and thermosetting composition)

In 38 μm of thickness of PET film, each composition shown in table 7~12, In are coated with 120 μm of the applicator in gap It is 10 minutes dry in 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, in In the A test piece for the IPC MULTI-PURPOSE TEST BOARDB-25 that 1.6mm thickness FR-4 substrate is formed with 35 μm of copper thickness, benefit It is crimped 60 seconds with vacuum laminator with the condition of 60 DEG C, pressure 0.5MPa, is laminated the resin layer of each composition, utilizes printed circuit Plate is with metal halide lamp exposure machine with 700mJ/cm²After carrying out whole face exposure, PET film is removed, 30 DEG C of 1wt% is used Na₂CO₃Developer solution, with developing machine develop 60 seconds.Later, heating 60 minutes in heated air circulation type drying oven in 150 DEG C makes it Solidification.Then, according to permanganic acid de-smear (ATOTECH corporation), electroless copper (Thru-Cup PEA, upper industrial group, village System), the sequence of cathode copper plating handled, implement 25 μm of copper thickness of copper plating.Then, in heated air circulation type Make annealing treatment within 60 minutes in 190 DEG C in drying oven, obtains the test substrate for implementing copper plating.Then, it will shape For diameter 1cm circle acidproof adhesive tape by become A test piece center in a manner of be attached at copper plating be covered with, with 40 DEG C of 40 mass % Ferric chloride in aqueous solution, by the etching removal of the copper plating other than the acidproof tape portion on resin cured matter.Then, circular Copper plating is covered with and loads onto electric wire with wire bonding material and soldering iron, for IPC MULTI-PURPOSE TEST BOARD wiring similarly Electric wire is loaded onto, regard circle as anode, wiring is regard as cathode, applies the voltage of 3.3V, carried out in the environment of 130 DEG C 85% Test in 200 hours.Test film makes 10 for each composition.At this point, often measuring insulation resistance, 1 × 10 will be become⁶Ω NG is evaluated as at the time of following.It all will be evaluated as ◎ without NG person until off-test, 1~4 NG person is evaluated as to zero, by 5 ~9 NG persons be evaluated as △, will all be evaluated as NG person ×.Show the results of the evaluation table 7~12.

[comb-type electrode insulating reliability]

(heat-curable composition)

In 38 μm of thickness of PET film, each composition shown in table 4~6, In are coated with 120 μm of the applicator in gap It is 10 minutes dry in 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, in In the A test piece for the IPC MULTI-PURPOSE TEST BOARD B-25 that 1.6mm thickness FR-4 substrate is formed with 35 μm of copper thickness, It is crimped 60 seconds using vacuum laminator with the condition of 60 DEG C, pressure 0.5MPa, is laminated the resin layer of each composition, removing PET is thin Film, heating 30 minutes in heated air circulation type drying oven in 180 DEG C makes its solidification.Then, IPC MULTI-PURPOSE is cut off The lower end of TEST BOARD B-25 (is cut off) as electrically independent terminal with the dotted line part of Fig. 2-4.Then, make A test piece Top is cathode, lower part is anode to apply the voltage of 50V, and test in 200 hours is carried out in the environment of 130 DEG C, 85%.Examination It tests piece and 10 is made to each composition.At this point, often measuring insulation resistance.As 1 × 10⁶NG is set as at the time of Ω or less.It will It all is evaluated as ◎ without NG person until off-test, 1~4 NG person is evaluated as zero, 5~9 NG persons are evaluated as △, it will All be evaluated as NG person ×.Show the results of the evaluation table 4~6.

(Photosetting and thermosetting composition)

In 38 μm of thickness of PET film, each composition shown in table 7~12, In are coated with 120 μm of the applicator in gap It is 10 minutes dry in 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, in In the A test piece for the IPC MULTI-PURPOSE TEST BOARD B-25 that 1.6mm thickness FR-4 substrate is formed with 35 μm of copper thickness, It is crimped 60 seconds using vacuum laminator with the condition of 60 DEG C, pressure 0.5MPa, is laminated the resin layer of each composition, utilize printing electricity Road plate is with metal halide lamp exposure machine with 700mJ/cm²After carrying out whole face exposure, PET film is removed, uses 30 DEG C 1wt%Na₂CO₃Developer solution, with developing machine develop 60 seconds.Later, 60 points are heated in 150 DEG C in heated air circulation type drying oven Clock makes its solidification.Then, the lower end for cutting off IPC MULTI-PURPOSE TEST BOARD B-25, as electrically independent end Son.Then, making the top cathode of A test piece, lower part is anode to apply the voltage of 50V, in the environment of 130 DEG C, 85% into Row test in 200 hours.Test film makes 10 to each composition.At this point, often measuring insulation resistance, become 1 × 10⁶Ω with NG will be set as at the time of lower.It all is evaluated as ◎ without NG person until near off-test, 1~4 NG person is evaluated as to zero, by 5~9 A NG person be evaluated as △, will all be evaluated as NG person ×.Show the results of the evaluation table 7~12.

[resistance to soldering heat performance]

(heat-curable composition)

It is on the FR-4 copper-clad laminated board of size 150mm × 95mm, 1.6mm thickness, each composition is inclined with 80 mesh Supreme Being's Telons Version silk-screen printing is pressed to form whole face solid pattern, it is 30 minutes dry with 80 DEG C in heated air circulation type drying oven, then, 180 It is heating and curing at DEG C 30 minutes, obtains test film.Rosin series scaling powder, In are coated in the solidfied material side of the composition of the test film 260 DEG C of solder laminar flow 60 seconds, is cleaned with propylene glycol monomethyl ether, is then cleaned with ethyl alcohol.For test film, with Visually expansion, removing, the variation of surface state of observation film.By film can be observed expansion, removing, by surface dissolution, Abnormal situation caused by softening etc. is evaluated as ×, above-mentioned abnormal situation will be not observed and be evaluated as zero.By evaluation result It is shown in table 4~6.

(Photosetting and thermosetting composition)

It is on the FR-4 copper-clad laminated board of size 150mm × 95mm, 1.6mm thickness, each composition is inclined with 80 mesh Supreme Being's Telons Version silk-screen printing is pressed to form whole face solid pattern, it is 30 minutes dry with 80 DEG C in heated air circulation type drying oven, use printed circuit Plate is with metal halide lamp exposure machine with 700mJ/cm²Whole face exposure is carried out, 30 DEG C of 1wt%Na is used₂CO₃Developer solution, use Developing machine develops 60 seconds.Later, it is heating and curing 60 minutes in heated air circulation type drying oven in 150 DEG C, obtains test film.To this The solidfied material side of the composition of test film is coated with rosin series scaling powder, solder laminar flow 60 seconds of 260 DEG C, with propylene glycol list first The cleaning of base ether acetic acid ester, is then cleaned with ethyl alcohol.For test film, visually to observe the expansion of film, removing, surface state Variation.By film can be observed situation abnormal caused by expansion, removing, the dissolution as surface, softening etc. be evaluated as ×, will not have Have and observes that above-mentioned abnormal situation is evaluated as zero.Show the results of the evaluation table 7~12.

[production of thermal expansion measurement sample]

(hot curing resin composition)

Each composition shown in applicator coating table 4~6 in 38 μm of thickness of PET film with 120 μm of gap, in heat It is 10 minutes dry in 90 DEG C in wind circulating drying oven, obtain the dry film with the resin layer of each composition.Later, in thickness 18 μm copper foil on crimped 60 seconds with vacuum laminator with the condition of 60 DEG C, pressure 0.5MPa, be laminated the resin layer of each composition, shell From PET film.Then, heating in heated air circulation type drying oven in 180 DEG C makes its solidification for 30 minutes, removes copper foil, consolidate Change the sample of film.

(light solidifying/heat solidifying resin composition)

18 μm of copper foil of thickness is attached on the FR-4 copper-clad laminated board of thickness 1.6mm, with 120 μm of the applicator in gap It is coated with each composition shown in table 7~12, it is 10 minutes dry in 90 DEG C in heated air circulation type drying oven.Later, make with 3mm The negative mask of width × 30mm long pattern is closely sealed, with printed circuit board metal halide lamp exposure machine with 700mJ/cm²Into Row exposure.Then, using 30 DEG C of 1wt%Na₂CO₃Developer solution, with developing machine develop 60 seconds.Later, dry in heated air circulation type Heating in dry furnace in 150 DEG C makes its solidification for 60 minutes, removes copper foil, obtains the sample of cured film.

[measurement of coefficient of thermal expansion]

(hot curing resin composition)

The thermal expansion measurement of production is cut into 3mm wide × 30mm long with sample.Use TA Instrument corporation TMA (Thermomechanical Analysis) Q400 is by the test film with 16mm, load 30mN, nitrogen between stretch mode and chuck 250 DEG C are warming up under atmosphere, with 5 DEG C/min from 20 DEG C, then, 20 DEG C is cooled to from 250 DEG C with 5 DEG C/min and is measured.It asks Average coefficient of thermal expansion α 1 from 30 DEG C to 100 DEG C when the cooling down out and average coefficient of thermal expansion α 2 from 200 DEG C to 230 DEG C.By its As a result it is shown in table 4~6.

(light solidifying/heat solidifying resin composition)

Other than the sample of direct use production, carried out with method same as hot curing resin composition.By its As a result it is shown in table 7~12.

[table 4]

* 2-1) heat-curing resin 2-1:Epiclon HP-4032DIC Co. Ltd. system solid component 50 mass % ring Hexanone varnish (cyclic ether compound with naphthalene skeleton)

* 2-2) heat-curing resin 2-2:NC-7300L Nippon Kayaku K. K solid component 50 mass % hexamethylene Ketone varnish (cyclic ether compound with naphthalene skeleton)

* 2-3) heat-curing resin 2-3:YX-8800 Mitsubishi chemical Co., Ltd solid component 50 mass % hexamethylene Ketone varnish (cyclic ether compound with anthracene skeleton)

* 2-4) heat-curing resin 2-4:Epiclon N-740 Dainippon Ink Chemicals solid component 50 mass % ring Hexanone varnish

* 2-5) 830 Dainippon Ink Chemicals's system of heat-curing resin 2-5:Epiclon

* 2-6) heat-curing resin 2-6:JER827 Mitsubishi chemical Co., Ltd system

* 2-7) heat-curing resin 2-7:HF-1 is bright and is melted into 60 mass % cyclohexanone varnish of Co. Ltd. system solid component

* 2-8) curing catalysts 2-1:2E4MZ (2-ethyl-4-methylimidazole) Shikoku Chem system

* 2-9) filler 2-1:Adma Fine SO-C2 Co., Ltd.'s Admatechs system (silica)

* 2-10) organic solvent 2-1: dimethylformamide

* 2-11) defoaming agent 2-1:BYK-352 BYK Chemie JAPAN Co. Ltd. system

[table 5]

[table 6]

* 2-18) filler 2-2:B-30 Sakai Chemical Industry Co., Ltd. Sulphuric acid barium

* 2-19) filler 2-3:DAW-07Denka Co. Ltd. system aluminium oxide

* 2-20) dispersing agent 2-1:DISPERBYK-111 BYK Chemie corporation

[table 7]

* 2-12) curing catalysts 2-2: Crushing of Ultrafine melamine Misao Kusano system

* 2-13) curing catalysts 2-3: dicyandiamide

* 2-14) Photoepolymerizationinitiater initiater 2-1:Irgacure 907BASF Co. Ltd. system

* 2-15) light-cured resin 2-1: dipentaerythritol tetraacrylate

* 2-16) heat-curing resin 2-8:TEPIC-H (triglycidyl isocyanurate) Misao Kusano system

* 2-17) colorant 2-1: phthalocyanine blue

[table 8]

[table 9]

[table 10]

[table 11]

[table 12]

The result as documented by table 4~12 can clearly confirm, by the inclusion of fine as fine cellulose fiber Powder and with the cyclic ether compound of at least any one in naphthalene skeleton and anthracene skeleton, can obtain interlayer, it is interelectrode absolutely The insulating reliability of edge reliability, particularly interlayer is excellent and has the hardening resin composition of low thermal expansion rate.In addition, It confirmed by the evaluation result of resistance to soldering heat performance, the heat resistance of each composition of embodiment, chemical resistance are excellent, can It is used as wiring plate with composition.

<3rd embodiment>

As fine cellulose fiber CNF1~CNF3 and Cellulose nanocrystal particle CNC1, CNC2, using with it is first real The same Production Example 1~5 of example is applied, as 1~varnish of varnish 3, uses synthesis example 1~3 same as second embodiment.

According to the record in following table 1 3~21, after each ingredient is stirred in compounding, the high pressure using the mechanical industrial system of Jitian is equal Change device Nanovater NVL-ES008, being repeated 6 times makes its dispersion, prepares each composition.It should be noted that in table 13~21 Numerical value indicate mass parts.

[copper-plated peel strength]

(heat-curable composition)

Each composition shown in applicator coating table 13~15 in 38 μm of thickness of PET film with 120 μm of gap, In It is 10 minutes dry in 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, with The size of 150mm × 100mm on the FR-4 copper-clad laminated board (copper thick 18 μm) of thickness 1.6mm with vacuum laminator with 60 DEG C, The condition of pressure 0.5MPa crimps 60 seconds, is laminated the resin layer of each composition, removes PET film, uses heated air circulation type drying oven Heating 30 minutes at 180 DEG C makes its solidification.Then, according to permanganic acid de-smear (ATOTECH corporation), electroless copper (Thru- Cup PEA, upper industrial group, village system), the sequence of cathode copper plating handled, implement at 25 μm of copper thickness of copper plating Reason.Then, make annealing treatment within 60 minutes with 190 DEG C in heated air circulation type drying oven, obtain implementing copper plating Test substrate.Test substrate is cut out with 1cm wide, long 7cm or more, using Shimadzu Seisakusho Ltd. small desk testing machine EZ-SX, Using 90 ° of printing peel jigs, find out with the peel strength of 90 degree of angle removing.For evaluation, 4.5N/m or more person is set It is zero, 2.5N/m is evaluated as △ more than and less than 4.5N/m person, will be evaluated as less than 2.5N/m person ×.It the results are shown in table 13~15.It should be noted that thinking that if peel strength is 4.5N/m or more, even the circuit of fine, is not also shelled From the problem of.The benchmark is quite stringent evaluation condition.

(Photosetting and thermosetting composition)

Each composition shown in applicator coating table 16~21 in 38 μm of thickness of PET film with 120 μm of gap, In It is 10 minutes dry in 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, with The size of 150mm × 100mm on the FR-4 copper-clad laminated board (copper thick 18 μm) of thickness 1.6mm with vacuum laminator with 60 DEG C, The condition of pressure 0.5MPa crimps 60 seconds, is laminated the resin layer of each composition, is exposed with printed circuit board with metal halide lamp Machine is with 700mJ/cm²After carrying out whole face exposure, PET film is removed, 30 DEG C of 1wt%Na is used₂CO₃Developer solution, use developing machine Development 60 seconds.Later, being heated 60 minutes with heated air circulation type drying oven in 150 DEG C makes its solidification.Then, glue is removed according to permanganic acid Slag (ATOTECH corporation), electroless copper (Thru-Cup PEA, upper industrial group, village system), the sequence of cathode copper plating It is handled, implements 25 μm of copper thickness of copper plating.Then, 60 points are carried out in 190 DEG C in heated air circulation type drying oven Clock annealing, obtains the test substrate for implementing copper plating.Test substrate is cut out with 1cm wide, long 7cm or more, is made It is found out with Shimadzu Seisakusho Ltd. small desk testing machine EZ-SX using 90 ° of printing peel jigs with 90 degree of angle removing Peel strength.For evaluation, 4.5N/m or more person is set as zero, 2.5N/m is set as △ more than and less than 4.5N/m person, it will be small Be set as in 2.5N/m ×.It the results are shown in table 16~21.

[resistance to soldering heat performance]

(heat-curable composition)

On the FR-4 copper-clad laminated board of size 150mm × 95mm, 1.6mm thickness, by each composition shown in table 13~15 Whole face solid pattern is formed with 80 mesh Supreme Being's Telon bias version silk-screen printings, it is 30 points dry in 80 DEG C in heated air circulation type drying oven Clock is then heating and curing 30 minutes at 180 DEG C, has obtained test film.It is coated in the solidfied material side of the composition of the test film Rosin series scaling powder is cleaned solder laminar flow 60 seconds of 260 DEG C with propylene glycol monomethyl ether, then, clear with ethyl alcohol It washes.For test film, visually to observe the expansion, removing, the variation of surface state of film.Film observe expansion, removing, by Abnormal situation caused by dissolution, the softening on surface etc. is evaluated as ×, above-mentioned abnormal situation will be not observed and be evaluated as zero. Show the results of the evaluation table 13~15.

(Photosetting and thermosetting composition)

On the FR-4 copper-clad laminated board of size 150mm × 95mm, 1.6mm thickness, by each composition shown in table 16~21 Whole face solid pattern is formed with 80 mesh Supreme Being's Telon bias version silk-screen printings, it is 30 points dry in 80 DEG C in heated air circulation type drying oven Clock, with printed circuit board metal halide lamp exposure machine with 700mJ/cm²Whole face exposure is carried out, 30 DEG C of 1wt% is used Na₂CO₃Developer solution, with developing machine develop 60 seconds.Later, it is heating and curing 60 points in heated air circulation type drying oven in 150 DEG C Clock obtains test film.It is coated with rosin series scaling powder in the solidfied material side of the composition of the test film, in 260 DEG C of solder laminar flow It is 60 seconds dynamic, it is cleaned with propylene glycol monomethyl ether, is then cleaned with ethyl alcohol.For test film, visually to observe film Expansion, removing, the variation of surface state.It is different caused by observing expansion, removing, the dissolution as surface, softening etc. in film Normal situation is evaluated as ×, above-mentioned abnormal situation will be not observed and be evaluated as zero.Show the results of the evaluation table 16~21.

[insulating properties]

(heat-curable composition)

Each composition shown in applicator coating table 13~15 in 38 μm of thickness of PET film with 120 μm of gap, In It is 10 minutes dry in 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, In In the A test piece of the IPC MULTI-PURPOSE TEST BOARD B-25 formed on 1.6mm thickness FR-4 substrate with 35 μm of copper thickness It is crimped 60 seconds with vacuum laminator with the condition of 60 DEG C, pressure 0.5MPa, is laminated the resin layer of each composition, removes PET film, Heating 30 minutes in heated air circulation type drying oven in 180 DEG C makes its solidification.Then, IPC MULTI-PURPOSE TEST is cut off The lower end of BOARD B-25 (is cut off) as electrically independent terminal with the dotted line part of Fig. 3-2.Then, make the top of A test piece The bias that cathode, lower part are anode to apply DC500V, measures insulating resistance value.It is 100G by insulating resistance value for evaluation The situation of Ω or more is set as zero, by insulating resistance value be less than 100G Ω the case where be set as ×.Show the result in table 13~15.

(Photosetting and thermosetting composition)

In 38 μm of thickness of PET film, it is coated with each composition shown in table 16~21 with 120 μm of the applicator in gap, It is 10 minutes dry in 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, In In the A test piece of the IPC MULTI-PURPOSE TEST BOARD B-25 formed on 1.6mm thickness FR-4 substrate with 35 μm of copper thickness It is crimped 60 seconds with vacuum laminator with the condition of 60 DEG C, pressure 0.5MPa, is laminated the resin layer of each composition, uses printed circuit board With metal halide lamp exposure machine with 700mJ/cm²After carrying out whole face exposure, PET film is removed, 30 DEG C of 1wt% is used Na₂CO₃Developer solution, with developing machine develop 60 seconds.Later, heating 60 minutes in heated air circulation type drying oven in 150 DEG C makes it Solidification.Then, the lower end for cutting off IPC MULTI-PURPOSE TEST BOARD B-25, as electrically independent terminal.So Afterwards, making the top cathode of A test piece, lower part is anode to apply the bias of DC500V, measures insulating resistance value.For evaluating, By insulating resistance value be 100G Ω or more situation be set as zero, by insulating resistance value be less than 100G Ω the case where be set as ×.It will knot Fruit shown in table 1 6~21.

[relative dielectric constant, dielectric loss angle tangent]

(heat-curable composition)

Each composition shown in applicator coating table 13~15 in 38 μm of thickness of PET film with 200 μm of gap, In It is 20 minutes dry in 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, make thickness The gloss of 18 μm of electrolytic copper foil is face-up, is fixed on the FR-4 copper-clad laminated board of thickness 1.6mm with adhesive tape, in obtained base On material, is crimped 60 seconds with vacuum laminator with the condition of 60 DEG C, pressure 0.5MPa, be laminated the resin layer of each composition, remove PET Film, heating 30 minutes in heated air circulation type drying oven in 180 DEG C makes its solidification.Then, fixed adhesive tape, removing electricity are removed Copper foil is solved, cuts out the size of 1.7mm × 100mm as sample for evaluation.Measurement is empty using Northeast the development of electronics applied corporation Chamber resonator (5GHz), with Keysight Technologies corporation Network analyzer E-507 progress.For phase Evaluation to dielectric constant will measure the case where 3 average value is less than 2.8 and be set as zero, by 2.8 feelings more than and less than 3.0 Condition is set as △, 3.0 or more situation is set as ×.The average value for measuring 3 times is less than by the evaluation for dielectric loss angle tangent 0.02 the case where, is set as zero, 0.02 or more situation is set as ×.By each result shown in table 1 3~15.

(Photosetting and thermosetting composition)

Each composition shown in applicator coating table 16~21 in 38 μm of thickness of PET film with 200 μm of gap, In It is 30 minutes dry in 80 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, make thickness The gloss of 18 μm of electrolytic copper foil is face-up, is fixed on the FR-4 copper-clad laminated board of thickness 1.6mm with adhesive tape, in obtained base On material, is crimped 60 seconds with vacuum laminator with the condition of 60 DEG C, pressure 0.5MPa, be laminated the resin layer of each composition, use The aperture mask of 1.7mm × 100mm, with printed circuit board metal halide lamp exposure machine with 700mJ/cm²After being exposed, PET film is removed, 30 DEG C of 1wt%Na is used₂CO₃Developer solution, with developing machine develop 60 seconds.Later, dry with heated air circulation type Dry furnace heats 60 minutes in 150 DEG C makes its solidification.Then, fixed adhesive tape is removed, electrolytic copper foil is removed, as evaluation sample Product.Measurement uses Northeast the development of electronics applied corporation cavity resonator (5GHz), with Keysight Technologies company Network analyzerE-507 processed is carried out.Evaluation for relative dielectric constant will measure 3 average value less than 3.0 Situation is set as zero, and by 3.0 more than and less than 3.2 the case where is set as △, 3.2 or more situation is set as ×.For dielectric loss The evaluation of angle tangent will measure the case where 3 average value is less than 0.02 and be set as zero, 0.02 or more situation is set as ×.It will Each result shown in table 1 6~21.

[table 13]

* 3-1) heat-curing resin 3-1:Epiclon HP-7200 solid component 50 the cyclohexanone varnish of mass % (have The cyclic ether compound of bicyclopentadiene skeleton)

* 3-2) heat-curing resin 3-2:Tactix756 solid component 50 mass % cyclohexanone varnish (have two rings penta The cyclic ether compound of diene skeleton)

* 3-3) heat-curing resin 3-3:Epiclon N-740 Dainippon Ink Chemicals solid component 50 mass % ring Hexanone varnish

* 3-4) 830 Dainippon Ink Chemicals's system of heat-curing resin 3-4:Epiclon

* 3-5) heat-curing resin 3-5:JER827 Mitsubishi chemical Co., Ltd system

* 3-6) heat-curing resin 3-6:Resitop GDP-6085 solid component 60 mass % cyclohexanone varnish (have The phenolic resin of bicyclopentadiene skeleton)

* 3-7) heat-curing resin 3-7:HF-1 is bright and is melted into 60 mass % cyclohexanone varnish of Co. Ltd. system solid component

* 3-8) curing catalysts 3-1:2E4MZ (2-ethyl-4-methylimidazole) Shikoku Chem system

* 3-9) filler 3-1:Adma Fine SO-C2 Co., Ltd.'s Admatechs system (silica)

* 3-10) organic solvent 3-1: dimethylformamide

* 3-11) defoaming agent 3-1:BYK-352BYK Chemie JAPAN Co. Ltd. system

[table 14]

[table 15]

* 3-18) filler 3-2:B-30 Sakai Chemical Industry Co., Ltd. Sulphuric acid barium

* 3-19) filler 3-3:DAW-07 Denka Co. Ltd. system aluminium oxide

* 3-20) dispersing agent 3-1:DISPERBYK-111BYK Chemie corporation

[table 16]

* 3-12) curing catalysts 3-2: Crushing of Ultrafine melamine Misao Kusano system

* 3-13) curing catalysts 3-3: dicyandiamide

* 3-14) 907 BASF Co. Ltd. system of Photoepolymerizationinitiater initiater 3-1:Irgacure

* 3-15) light-cured resin 3-1: dipentaerythritol tetraacrylate

* 3-16) heat-curing resin 3-8:TEPIC-H (triglycidyl isocyanurate) Misao Kusano system

* 3-17) colorant 3-1: phthalocyanine blue

[table 17]

[table 18]

[table 19]

[table 20]

[table 21]

Can clearly it be confirmed by the result recorded in table 13~21, by the inclusion of fine as fine cellulose fiber Powder and selected from by the cyclic ether compound with bicyclopentadiene skeleton and with the phenolic resin group of bicyclopentadiene skeleton At group in it is at least one kind of, can obtain insulating reliability is excellent, have low dielectric property and solidfied material with it is copper-plated closely sealed The good hardening resin composition of property.In addition, confirmed by the evaluation result of resistance to soldering heat performance, each composition of embodiment Heat resistance, chemical resistance it is excellent, can be used as wiring plate and used with composition.

<fourth embodiment>

As fine cellulose fiber CNF1~CNF3 and Cellulose nanocrystal particle CNC1, CNC2, using with it is first real The same Production Example 1~5 of example is applied, as 1~varnish of varnish 3, uses synthesis example 1~3 same as second embodiment.

The high pressure of the mechanical industrial system of Jitian is used after the compounding stirring of each ingredient according to the record in following table 2 2~30 Homogenizer Nanovater NVL-ES008, being repeated 6 times makes its dispersion, prepares each composition.It should be noted that table 22~30 In numerical value indicate mass parts.

[resistance to soldering heat performance]

(heat-curable composition)

On the FR-4 copper-clad laminated board of size 150mm × 95mm, 1.6mm thickness, by each composition shown in table 22~25 Whole face solid pattern is formed with 80 mesh Supreme Being's Telon bias version silk-screen printings, it is 30 points dry in 80 DEG C in heated air circulation type drying oven Clock is then heating and curing 30 minutes in 180 DEG C, obtains test film.Rosin is coated in the solidfied material side of the composition of the test film It is scaling powder, solder laminar flow 60 seconds of 260 DEG C, is cleaned with propylene glycol monomethyl ether, then cleaned with ethyl alcohol.It is right In test film, visually to observe the expansion, removing, the variation of surface state of film.Will film observe expansion, removing, by Abnormal situation caused by dissolution, the softening on surface etc. is evaluated as ×, above-mentioned abnormal situation will be not observed and be evaluated as zero. Show the results of the evaluation table 22~25.

(Photosetting and thermosetting composition)

On the FR-4 copper-clad laminated board of size 150mm × 95mm, 1.6mm thickness by each composition shown in table 26~30 with 80 mesh Supreme Being's Telon bias version silk-screen printings form whole face solid pattern, make it dry 30 in 80 DEG C in heated air circulation type drying oven Minute, with printed circuit board metal halide lamp exposure machine with 700mJ/cm²Whole face exposure is carried out, 30 DEG C of 1wt% is used Na₂CO₃Developer solution, with developing machine develop 60 seconds.Later, it is heating and curing 60 points in heated air circulation type drying oven in 150 DEG C Clock obtains test film.It is coated with rosin series scaling powder in the solidfied material side of the composition of the test film, in 260 DEG C of solder laminar flow It is 60 seconds dynamic, it is cleaned with propylene glycol monomethyl ether, is then cleaned with ethyl alcohol.For test film, visually to observe film Expansion, removing, the variation of surface state.It is different caused by observing expansion, removing, the dissolution as surface, softening etc. in film Normal situation is evaluated as ×, it will not observe that above-mentioned abnormal situation is evaluated as zero.Show the results of the evaluation table 26~30.

[insulating properties]

(heat-curable composition)

Each composition shown in applicator coating table 22~25 in 38 μm of thickness of PET film with 120 μm of gap, In It is 10 minutes dry in 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, In In the A test piece for the IPC MULTI-PURPOSE TEST BOARD B-25 that 1.6mm thickness FR-4 substrate is formed with 35 μm of copper thickness, It is crimped 60 seconds with vacuum laminator with the condition of 60 DEG C, pressure 0.5MPa, is laminated the resin layer of each composition, removes PET film, Heating 30 minutes in heated air circulation type drying oven in 180 DEG C makes its solidification.Then, IPC MULTI-PURPOSE TEST is cut off The lower end of BOARD B-25 (is cut off) as electrically independent terminal with the dotted line part of Fig. 4-2.Then, make the top of A test piece The bias that cathode, lower part are anode to apply DC500V, measures insulating resistance value.It is 100G by insulating resistance value for evaluation The situation of Ω or more is set as zero, by insulating resistance value be less than 100G Ω the case where be set as ×.Show the result in table 22~25.

(Photosetting and thermosetting composition)

Each composition shown in applicator coating table 26~30 in 38 μm of thickness of PET film with 120 μm of gap, In It is 10 minutes dry in 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, In In the A test piece for the IPC MULTI-PURPOSE TEST BOARD B-25 that 1.6mm thickness FR-4 substrate is formed with 35 μm of copper thickness, It is crimped 60 seconds with vacuum laminator with the condition of 60 DEG C, pressure 0.5MPa, is laminated the resin layer of each composition, uses printed circuit board With metal halide lamp exposure machine with 700mJ/cm²After carrying out whole face exposure, PET film is removed, 30 DEG C of 1wt% is used Na₂CO₃Developer solution, with developing machine develop 60 seconds.Later, being heated with heated air circulation type drying oven in 150 DEG C makes it solid for 60 minutes Change.Then, the lower end for cutting off IPC MULTI-PURPOSE TEST BOARD B-25, as electrically independent terminal.Then, Making the top cathode of A test piece, lower part is anode to apply the bias of DC500V, measures insulating resistance value.It, will be exhausted for evaluation Edge resistance value be 100G Ω or more situation be set as zero, by insulating resistance value be less than 100G Ω the case where be set as ×.Result is shown In table 26~30.

[removal of glue residue]

(hot curing resin composition)

Each composition shown in applicator coating table 22~25 in 38 μm of thickness of PET film with 120 μm of gap, In It is 10 minutes dry with 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, with The size of 150mm × 100mm on the FR-4 copper-clad laminated board (copper thick 18 μm) of thickness 1.6mm, with vacuum laminator with 60 DEG C, The condition of pressure 0.5MPa crimps 60 seconds, is laminated the resin layer of each composition, PET film is removed, in heated air circulation type drying oven In heated in 180 DEG C and make its solidification in 30 minutes, obtain test film.

To test film with carbon dioxide laser drilling machine LC-2K212 (Hitachi's Via mechanics Co. Ltd. system) with light 100 μm of apertures of beam diameter.Then, permanganic acid de-smear (ATOTECH corporation) is carried out.The standard procedure of de-smear is swelling work The sequence of sequence (60 DEG C 5 points), permanganic acid etching work procedure (80 DEG C 20 minutes), neutralization step (40 DEG C 5 minutes), but permanganic acid etches In process, be divided into 10 minutes, 15 minutes, 20 minutes 3 stages were tested.

Then, it for bore portion, uses scanning electron microscope JSM-6610LV (Jeol Ltd.'s system) It is observed again with multiplying power 3500, confirms the presence or absence of the glue residue on copper surface.For evaluation, the permanganic acid etching with 10 minutes is not had The case where having the case where glue residue to be set as zero, not having glue residue with 15 minutes, is set as △, is set finally without the case where glue residue with 20 minutes For ×.Show the result in table 22~25.

(light solidifying/heat solidifying resin composition)

In 38 μm of thickness of PET film, it is coated with each composition shown in table 26~30 with 120 μm of the applicator in gap, It is 10 minutes dry in 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, with The size of 150mm × 100mm on the FR-4 copper-clad laminated board (copper thick 18 μm) of thickness 1.6mm with vacuum laminator with 60 DEG C, The condition of pressure 0.5MPa crimps 60 seconds, is laminated the resin layer of each composition, is exposed with printed circuit board with metal halide lamp Machine is with 700mJ/cm²After carrying out whole face exposure, PET film is removed, 30 DEG C of 1wt%Na is used₂CO₃Developer solution, use developing machine Development 60 seconds.Later, heating 60 minutes in heated air circulation type drying oven in 150 DEG C makes its solidification, obtains test film.

To test film with carbon dioxide laser drilling machine LC-2K212 (Hitachi's Via mechanics Co. Ltd. system) with light 100 μm of apertures of beam diameter.Then, using permanganic acid de-smear (ATOTECH corporation), in permanganic acid etching work procedure, it is divided into 10 minutes, 15 minutes, 20 minutes 3 stages were tested.

Then, it for bore portion, uses scanning electron microscope JSM-6610LV (Jeol Ltd.'s system) It is observed again with multiplying power 3500, confirms the presence or absence of the glue residue on copper surface.For evaluation, the permanganic acid etching with 10 minutes is not had The case where having the case where glue residue to be set as zero, not having glue residue with 15 minutes, is set as △, is set finally without the case where glue residue with 20 minutes For ×.Show the result in table 26~30.

[measurement of peel strength and Ra]

(hot curing resin composition)

In 38 μm of thickness of PET film, it is coated with each composition shown in table 22~25 with 120 μm of the applicator in gap, It is 10 minutes dry in 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, with The size of 150mm × 100mm on the FR-4 copper-clad laminated board (copper thick 18 μm) of thickness 1.6mm with vacuum laminator with 60 DEG C, The condition of pressure 0.5MPa crimps 60 seconds, is laminated the resin layer of each composition, PET film is removed, in heated air circulation type drying oven In heated in 180 DEG C and make its solidification in 30 minutes.Then, using permanganic acid de-smear (ATOTECH corporation), permanganic acid etches work The time of sequence makes only 10 minutes samples in embodiment, and the sample of 10 minutes, 20 minute 2 stage is made in comparative example.Make For the roughness measurement on the surface of sample, Ra (arithmetic is measured using Guang Gan Wataru microscope Contour GT (BRUKER corporation) Mean roughness).Ra indicates arithmetic average roughness, crosses at the center of cross section curve, for the song that will be obtained by center line The value that the gross area on line is obtained divided by length, value more large roughness is bigger, and it is higher to be worth smaller flatness.It should be noted that Ra is provided in JIS B0031:2003.Show the result in table 22~25.

Then, for being completed to the test film of de-smear, according to electroless copper (Thru-Cup PEA, upper industrial group, village System), the sequence of cathode copper plating handled, implement 25 μm of copper thickness of copper plating.Then, in heated air circulation type Make annealing treatment within 60 minutes in 190 DEG C in drying oven, obtains the test substrate for implementing copper plating.Will test substrate with 1cm wide, long 7cm or more are cut out, using Shimadzu Seisakusho Ltd. small desk testing machine EZ-SX, using 90 ° of printing peel jigs, It finds out with the peel strength of 90 degree of angle removing.For evaluation, the situation of 4.5N/m or more is set as zero, by 2.5N/m or more And the case where being less than 4.5N/m, is set as △, will be set as less than the case where 2.5N/m ×.It the results are shown in table 22~25.

(light solidifying/heat solidifying resin composition)

In 38 μm of thickness of PET film, it is coated with each composition shown in table 26~30 with 120 μm of the applicator in gap, It is 10 minutes dry in 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, with The size of 150mm × 100mm on the FR-4 copper-clad laminated board (copper thick 18 μm) of thickness 1.6mm with vacuum laminator with 60 DEG C, The condition of pressure 0.5MPa crimps 60 seconds, is laminated the resin layer of each composition, is exposed with printed circuit board with metal halide lamp Machine is with 700mJ/cm²After carrying out whole face exposure, PET film is removed, 30 DEG C of 1wt%Na is used₂CO₃Developer solution, use developing machine Development 60 seconds.Later, heating 60 minutes in heated air circulation type drying oven in 150 DEG C makes its solidification.Then, it is removed using permanganic acid Glue residue (ATOTECH corporation), the time of permanganic acid etching work procedure make only 10 minutes samples in embodiment, in comparative example Make the sample of 10 minutes, 20 minute 2 stage.The roughness on the surface as sample measures, and uses Guang Gan Wataru microscope Contour GT (BRUKER corporation) measures Ra.Show the result in table 26~30.

Then, for being completed to the test film of de-smear, according to electroless copper (Thru-Cup PEA, upper industrial group, village System), the sequence of cathode copper plating handled, implement 25 μm of copper thickness of copper plating.Then, in heated air circulation type Make annealing treatment within 60 minutes in 190 DEG C in drying oven, obtains the test substrate for implementing copper plating.Will test substrate with 1cm wide, long 7cm or more are cut out, using Shimadzu Seisakusho Ltd. small desk testing machine EZ-SX, using 90 ° of printing peel jigs, It finds out with the peel strength of 90 degree of angle removing.For evaluation, the situation of 4.5N/m or more is set as zero, by 2.5N/m or more And the case where being less than 4.5N/m, is set as △, will be set as less than the case where 2.5N/m ×.It the results are shown in table 26~30.

[table 22]

* 4-1) phenoxy resin 4-1:YX6954 Mitsubishi chemical Co., Ltd solid component 30 mass % cyclohexanone it is clear Paint

* 4-2) phenoxy resin 4-2:1256 Mitsubishi chemical Co., Ltd solid component 30 mass % cyclohexanone varnish

* 4-3) phenoxy resin 4-3:4250 Mitsubishi chemical Co., Ltd solid component 30 mass % cyclohexanone varnish

* 4-4) heat-curing resin 4-1:Epiclon N-740 Dainippon Ink Chemicals solid component 50 mass % ring Hexanone varnish

* 4-5) 830 Dainippon Ink Chemicals's system of heat-curing resin 4-2:Epiclon

* 4-6) heat-curing resin 4-3:JER827 Mitsubishi chemical Co., Ltd system

* 4-7) heat-curing resin 4-4:HF-1 is bright and is melted into 60 mass % cyclohexanone varnish of Co. Ltd. system solid component

* 4-8) curing catalysts 4-1:2E4MZ (2-ethyl-4-methylimidazole) Shikoku Chem system

* 4-9) filler 4-1:Adma Fine SO-C2 Co., Ltd.'s Admatechs system (silica)

* 4-10) organic solvent 4-1: dimethylformamide

* 4-11) defoaming agent 4-1:BYK-352 BYK Chemie JAPAN Co. Ltd. system

[table 23]

[table 24]

* 4-18) filler 4-2:B-30 Sakai Chemical Industry Co., Ltd. Sulphuric acid barium

* 4-19) filler 4-3:DAW-07 Denka Co. Ltd. system aluminium oxide

* 4-20) dispersing agent 4-1:DISPERBYK-111 BYK Chemie corporation

[table 25]

* 4-12) curing catalysts 4-2: Crushing of Ultrafine melamine Misao Kusano system

* 4-13) curing catalysts 4-3: dicyandiamide

* 4-14) 907 BASF Co. Ltd. system of Photoepolymerizationinitiater initiater 4-1:Irgacure

* 4-15) light-cured resin 4-1: dipentaerythritol tetraacrylate

* 4-16) heat-curing resin 4-5:TEPIC-H (triglycidyl isocyanurate) Misao Kusano system

* 4-17) colorant 4-1: phthalocyanine blue

[table 26]

[table 27]

[table 28]

[table 29]

[table 30]

The result as documented by table 22~30 can be confirmed clearly, by the inclusion of fine as fine cellulose fiber Powder and phenoxy resin can obtain removing the glue residue generated by laser processing in de-smear process while having having Conducive to small surface roughness and the peel strength also excellent hardening resin composition of high-frequency transmission.In addition, by resistance to weldering The evaluation result for connecing hot property confirms, and the heat resistance of each composition of embodiment, chemical resistance are excellent, and being capable of conduct Wiring plate is used with composition.

<the 5th embodiment>

As fine cellulose fiber CNF1~CNF3 and Cellulose nanocrystal particle CNC1, CNC2, using with it is first real The same Production Example 1~5 of example is applied, as 1~varnish of varnish 3, uses synthesis example 1~3 same as second embodiment.

The high pressure of the mechanical industrial system of Jitian is used after the compounding stirring of each ingredient according to the record in following Table 3 1~39 Homogenizer Nanovater NVL-ES008, being repeated 6 times makes its dispersion, prepares each composition.It should be noted that table 31~39 In numerical value indicate mass parts.

[copper-plated expansion]

(heat-curable composition)

Each composition shown in applicator coating table 31~33 in 38 μm of thickness of PET film with 120 μm of gap, In It is 10 minutes dry in 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, with The size of 150mm × 100mm on the FR-4 copper-clad laminated board (copper thick 18 μm) of thickness 1.6mm with vacuum laminator with 60 DEG C, The condition of pressure 0.5MPa crimps 60 seconds, is laminated the resin layer of each composition, PET film is removed, in heated air circulation type drying oven In heated in 180 DEG C and make its solidification in 30 minutes.Then, according to permanganic acid de-smear (ATOTECH corporation), electroless copper (Thru-Cup PEA, upper industrial group, village system), the sequence of cathode copper plating are handled, and 25 μm of copper thickness of copper is implemented Plating.Then, make annealing treatment within 60 minutes in 190 DEG C in heated air circulation type drying oven, obtain implementing copper plating The test substrate of processing.Then, after passing through 3 times in 265 DEG C of peak temperature of reflow ovens, with the copper-plated expansion of visual valuation.It will Absolutely not expansion person is set as zero in test substrate 10, tests in substrate 10 and observes that expansion person is set as △ within 1, will Test substrate 10 in 2 or more observe expansion person be set as ×.Show the result in table 31~33.

(Photosetting and thermosetting composition)

Each composition shown in applicator coating table 34~39 in 38 μm of thickness of PET film with 120 μm of gap, In It is 10 minutes dry with 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, with The size of 150mm × 100mm on the FR-4 copper-clad laminated board (copper thick 18 μm) of thickness 1.6mm with vacuum laminator with 60 DEG C, The condition of pressure 0.5MPa crimps 60 seconds, is laminated the resin layer of each composition, is exposed with printed circuit board with metal halide lamp Machine is with 700mJ/cm²After carrying out whole face exposure, PET film is removed, 30 DEG C of 1wt%Na is used₂CO₃Developer solution, use developing machine Development 60 seconds.Later, heating 60 minutes in heated air circulation type drying oven in 150 DEG C makes its solidification.Then, it is removed according to permanganic acid Glue residue (ATOTECH corporation), electroless copper (Thru-Cup PEA, upper industrial group, village system), cathode copper plating it is suitable Sequence is handled, and 25 μm of copper thickness of copper plating is implemented.Then, 60 are carried out in 190 DEG C in heated air circulation type drying oven Minute annealing, obtains the test substrate for implementing copper plating.Then, pass through 3 in 265 DEG C of peak temperature of reflow ovens After secondary, with the copper-plated expansion of visual valuation.Absolutely not expansion person in substrate 10 will be tested and be set as zero, in test substrate 10 Observe that expansion person is set as △ within 1, will test substrate 10 in 2 or more observe expansion person be set as ×.Result is shown In table 34~39.

[resistance to soldering heat performance]

(heat-curable composition)

On the FR-4 copper-clad laminated board of size 150mm × 95mm, 1.6mm thickness, by each composition shown in table 31~33 Whole face solid pattern is formed with 80 mesh Supreme Being's Telon bias version silk-screen printings, it is 30 points dry in 80 DEG C in heated air circulation type drying oven Clock is then heating and curing 30 minutes at 180 DEG C, obtains test film.Rosin is coated in the solidfied material side of the composition of the test film It is scaling powder, solder laminar flow 60 seconds of 260 DEG C, is cleaned with propylene glycol monomethyl ether, then cleaned with ethyl alcohol.It is right In test film, visually to observe the expansion, removing, the variation of surface state of film.Expansion, removing are observed, by table in film Abnormal situation caused by dissolution, the softening in face etc. is evaluated as ×, it will not observe that above-mentioned abnormal situation is evaluated as zero.It will comment Valence result is shown in table 31~33.

(Photosetting and thermosetting composition)

On the FR-4 copper-clad laminated board of size 150mm × 95mm, 1.6mm thickness by each composition shown in table 34~39 with 80 mesh Supreme Being's Telon bias version silk-screen printings form whole face solid pattern, make it dry 30 in 80 DEG C in heated air circulation type drying oven Minute, with printed circuit board metal halide lamp exposure machine with 700mJ/cm²Whole face exposure is carried out, 30 DEG C of 1wt% is used Na₂CO₃Developer solution, with developing machine develop 60 seconds.Later, it is heating and curing 60 points in heated air circulation type drying oven in 150 DEG C Clock obtains test film.It is coated with rosin series scaling powder in the solidfied material side of the composition of the test film, in 260 DEG C of solder laminar flow It is 60 seconds dynamic, it is cleaned with propylene glycol monomethyl ether, is then cleaned with ethyl alcohol.For test film, visually to observe film Expansion, removing, the variation of surface state.It is different caused by observing expansion, removing, the dissolution as surface, softening etc. in film Normal situation is evaluated as ×, it will not observe that above-mentioned abnormal situation is evaluated as zero.Show the results of the evaluation table 34~39.

[insulating properties]

(heat-curable composition)

Each composition shown in applicator coating table 31~33 in 38 μm of thickness of PET film with 120 μm of gap, In It is 10 minutes dry in 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, In In the A test piece for the IPC MULTI-PURPOSE TEST BOARD B-25 that 1.6mm thickness FR-4 substrate is formed with 35 μm of copper thickness, It is crimped 60 seconds with vacuum laminator with the condition of 60 DEG C, pressure 0.5MPa, is laminated the resin layer of each composition, removes PET film, Heating 30 minutes in heated air circulation type drying oven in 180 DEG C makes its solidification.Then, IPC MULTI-PURPOSE TEST is cut off The lower end of BOARD B-25 (is cut off) as electrically independent terminal with the dotted line part of Fig. 5-2.Then, make the top of A test piece The bias that cathode, lower part are anode to apply DC500V, measures insulating resistance value.It is 100G by insulating resistance value for evaluation The situation of Ω or more is set as zero, by insulating resistance value be less than 100G Ω the case where be set as ×.Show the result in table 31~33.

(Photosetting and thermosetting composition)

Each composition shown in applicator coating table 34~39 in 38 μm of thickness of PET film with 120 μm of gap, In It is 10 minutes dry in 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, In In the A test piece for the IPC MULTI-PURPOSE TEST BOARD B-25 that 1.6mm thickness FR-4 substrate is formed with 35 μm of copper thickness, It is crimped 60 seconds with vacuum laminator with the condition of 60 DEG C, pressure 0.5MPa, is laminated the resin layer of each composition, uses printed circuit board With metal halide lamp exposure machine with 700mJ/cm²After carrying out whole face exposure, PET film is removed, 30 DEG C of 1wt% is used Na₂CO₃Developer solution, with developing machine develop 60 seconds.Later, heating 60 minutes in heated air circulation type drying oven in 150 DEG C makes it Solidification.Then, the lower end for cutting off IPC MULTI-PURPOSE TEST BOARD B-25, as electrically independent terminal.So Afterwards, making the top cathode of A test piece, lower part is anode to apply the bias of DC500V, measures insulating resistance value.For evaluating, By insulating resistance value be 100G Ω or more situation be set as zero, by insulating resistance value be less than 100G Ω the case where be set as ×.It will knot Fruit is shown in table 34~39.

[production of thermal expansion measurement sample]

(hot curing resin composition)

Each composition shown in table 31~33 is coated on the applicator in 120 μm of gap in 38 μm of thickness of PET film, It is 10 minutes dry with 90 DEG C in heated air circulation type drying oven, obtain the dry film with the resin layer of each composition.Later, in thickness It is crimped 60 seconds with vacuum laminator with the condition of 60 DEG C, pressure 0.5MPa on the copper foil of 18 μm of degree, is laminated the resin of each composition Layer removes PET film.Then, heating in heated air circulation type drying oven in 180 DEG C makes its solidification for 30 minutes, removes copper foil, obtains To the sample of cured film.

(light solidifying/heat solidifying resin composition)

18 μm of copper foil of thickness is attached on the FR-4 copper-clad laminated board of thickness 1.6mm, with 120 μm of the applicator in gap It is coated with each composition shown in table 34~39, it is 10 minutes dry in 90 DEG C in heated air circulation type drying oven.Later, make to have The negative mask of 3mm wide × 30mm long pattern is closely sealed, with printed circuit board metal halide lamp exposure machine with 700mJ/cm² Exposure.Then, using 30 DEG C of 1wt%Na₂CO₃Developer solution, with developing machine develop 60 seconds.Later, dry in heated air circulation type Heating in furnace in 150 DEG C makes its solidification for 60 minutes, removes copper foil, obtains the sample of cured film.

[measurement of coefficient of thermal expansion]

(hot curing resin composition)

The thermal expansion measurement of production is cut into 3mm wide × 30mm long with sample.For the test film, TA is used Instrument corporation TMA (Thermomechanical Analysis) Q400, with 16mm between stretch mode and chuck, negative 250 DEG C are warming up under lotus 30mN, nitrogen atmosphere, with 5 DEG C/min from 20 DEG C, then, is cooled to 20 DEG C with 5 DEG C/min from 250 DEG C It is measured.Find out 30 DEG C to 100 DEG C of the average coefficient of thermal expansion α 1 and 200 DEG C to 230 DEG C of average coefficient of thermal expansion α when cooling 2.In addition, being evaluated by value.α 1 is less than 25ppm person and is set as zero, 35ppm person will be less than and be set as △, 35ppm or more person is set For ×.α 2 is less than 75ppm person and is set as zero, 95ppm person will be less than and be set as △, 95ppm or more person is set as ×.Its result is shown In table 31~33.

(light solidifying/heat solidifying resin composition)

Other than the sample of direct use production, method same as hot curing resin composition is carried out.It is tied Fruit is shown in table 34~39.

[table 31]

* 5-1) heat-curing resin 5-1:NC-3000H Nippon Kayaku K. K solid component 50 mass % hexamethylene Ketone varnish (cyclic ether compound with biphenyl backbone)

* 5-2) heat-curing resin 5-2:YX-4000 Mitsubishi chemical Co., Ltd solid component 50 mass % hexamethylene Ketone varnish (cyclic ether compound with biphenyl backbone)

* 5-3) heat-curing resin 5-3:Epiclon N-740 Dainippon Ink Chemicals solid component 50 mass % ring Hexanone varnish

* 5-4) 830 Dainippon Ink Chemicals's system of heat-curing resin 5-4:Epiclon

* 5-5) heat-curing resin 5-5:JER827 Mitsubishi chemical Co., Ltd system

* 5-6) 60 mass % cyclohexanone of heat-curing resin 5-6:GPH-103 Nippon Kayaku K. K solid component Varnish (phenolic resin with biphenyl backbone)

* 5-7) heat-curing resin 5-7:HF-1 is bright and is melted into 60 mass % cyclohexanone varnish of Co. Ltd. system solid component

* 5-8) curing catalysts 5-1:2E4MZ (2-ethyl-4-methylimidazole) Shikoku Chem system

* 5-9) filler 5-1:Adma Fine SO-C2 Co., Ltd.'s Admatechs system (silica)

* 5-10) organic solvent 5-1: dimethylformamide

* 5-11) defoaming agent 5-1:BYK-352BYK Chemie JAPAN Co. Ltd. system

[table 32]

* 5-18) heat-curing resin 5-8: bisphenol-A diacetate esters Tokyo Chemical Industry Co., Ltd system (active ester chemical combination Object)

[table 33]

* 5-19) filler 5-2:B-30 Sakai Chemical Industry Co., Ltd. Sulphuric acid barium

* 5-20) filler 5-3:DAW-07 Denka Co. Ltd. system aluminium oxide

* 5-21) dispersing agent 5-1:DISPERBYK-111 BYK Chemie corporation

[table 34]

* 5-12) curing catalysts 5-2: Crushing of Ultrafine melamine Misao Kusano system

* 5-13) curing catalysts 5-3: dicyandiamide

* 5-14) 907 BASF Co. Ltd. system of Photoepolymerizationinitiater initiater 5-1:Irgacure

* 5-15) light-cured resin 5-1: dipentaerythritol tetraacrylate

* 5-16) heat-curing resin 5-9:TEPIC-H (triglycidyl isocyanurate) Misao Kusano system

* 5-17) colorant 5-1: phthalocyanine blue

[table 35]

[table 36]

[table 37]

[table 38]

[table 39]

The result as documented by table 31~39 can clearly confirm, by the inclusion of the fine powder as fine cellulose fiber Body and in the group being made of the cyclic ether compound with biphenyl backbone and the phenolic resin with biphenyl backbone at least 1 Kind, a kind of hardening resin composition can be obtained, can be obtained as low heat expansion, and on the solidfied material of composition with Solid shape is formed in copper-plated situation, and copper facing will not generate the solidfied material of expansion because of thermal history.In addition, by resistance to soldering heat performance Evaluation result confirmed that the heat resistance of each composition of embodiment, chemical resistance are excellent, and can as wiring plate use Composition uses.

<sixth embodiment>

As Cellulose nanocrystal particle CNC1, CNC2, Production Example 4,5 same as first embodiment is used.

According to the record in following table 40,41, after the compounding stirring of each ingredient, the high pressure using the mechanical industrial system of Jitian is equal Change device Nanovater NVL-ES008, being repeated 6 times makes its dispersion, prepares each composition.It should be noted that in table 40,41 Numerical value indicates mass parts.

Each composition obtained in Examples and Comparative Examples, evaluation coefficient of thermal expansion, heat resistance, insulating properties, toughness (are stretched Long rate), working life.Evaluation method is as follows described.

[coefficient of thermal expansion]

It is coated with each composition with the applicator in 120 μm of gap in 38 μm of thickness of PET film, it is dry in heated air circulation type It is 10 minutes dry in 90 DEG C in furnace, obtain the dry film with the resin layer of each composition.Later, it is used on 18 μm of thickness of copper foil Vacuum laminator crimps the resin layer for being laminated each composition for 60 seconds with the condition of 60 DEG C, pressure 0.5MPa, removes PET film.It connects , heating 30 minutes in heated air circulation type drying oven in 180 DEG C makes its solidification, removes from copper foil, obtains comprising each composition Solidfied material film sample.Gained film sample is cut into 3mm wide × 30mm long, as coefficient of thermal expansion measurement test film. About the test film, using TA Instrument corporation TMA (Thermomechanical Analysis) Q400, to stretch 250 DEG C are warming up under 16mm, load 30mN, nitrogen atmosphere, with 5 DEG C/min from 20 DEG C between mode and chuck, then, with 5 DEG C/minute Clock is cooled to 20 DEG C from 250 DEG C, measures coefficient of thermal expansion α 1 and α 2 (ppm/K).By their measurement result be shown in together table 40, 41。

[heat resistance]

It is coated with each composition with the applicator in 120 μm of gap in 38 μm of thickness of PET film, it is dry in heated air circulation type It is 10 minutes dry in 90 DEG C in furnace, obtain the dry film with the resin layer of each composition.Later, it is used on 18 μm of thickness of copper foil Vacuum laminator is crimped 60 seconds with the condition of 60 DEG C, pressure 0.5MPa, is laminated the resin layer of each composition, removes PET film.It connects , heating 30 minutes in heated air circulation type drying oven in 180 DEG C makes its solidification, removes from copper foil, obtains comprising each composition Solidfied material film sample.After gained film sample is crushed with the mortar of agate, according to JIS-K-7120, by with heating The TG curve that 10 DEG C/min of speed is measured under nitrogen stream confirms that 3 weight % heating weight reduces temperature and evaluates.For evaluation Benchmark, by 3 weight % heating weight reduce temperature be set as lower than 300 DEG C of persons ×, 300 DEG C of more than and less than 310 DEG C persons are set as 310 DEG C or more persons are set as 〇 by △.

[insulating properties]

It is coated with each composition with the applicator in 120 μm of gap in 38 μm of thickness of PET film, it is dry in heated air circulation type It is 10 minutes dry in 90 DEG C in furnace, obtain the dry film with the resin layer of each composition.Later, 1.6mm thickness FR-4 substrate with In the A test piece for the IPC MULTI-PURPOSE TEST BOARD B-25 that 35 μm of copper thickness is formed, with vacuum laminator with 60 DEG C, the condition of pressure 0.5MPa crimp 60 seconds, be laminated the resin layer of each composition, remove PET film, it is dry in heated air circulation type Heating 30 minutes in furnace in 180 DEG C makes its solidification.Then, it cuts off under IPC MULTI-PURPOSE TEST BOARD B-25 End (is cut off) as electrically independent terminal with the dotted line part of Fig. 6-4.Then, making the top cathode of A test piece, lower part is sun Extremely come the bias for applying DC500V, insulating resistance value is measured, is evaluated.

For evaluation criteria, it is that the above person of 100G Ω is set as zero by insulating resistance value, insulating resistance value is less than 100G Ω Person is set as ×.The evaluation result is shown in table 40,41 together.

[toughness]

It is coated with each composition with the applicator in 200 μm of gap in 38 μm of thickness of PET film, it is dry in heated air circulation type It is 20 minutes dry in 90 DEG C in furnace, obtain the dry film with the resin layer of each composition.Then, the thickness that gloss will be kept face-up 18 μm of electrolytic copper foil is fixed on the FR-4 copper-clad laminated board of thickness 1.6mm with adhesive tape, by aforementioned dry film vacuum laminator It is crimped 60 seconds with the condition of 60 DEG C, pressure 0.5MPa, the resin layer of each composition is laminated on aforementioned electrolytic copper foil, then, PET film is removed, heating 30 minutes in heated air circulation type drying oven in 180 DEG C solidifies resin layer.Then, it removes fixed Adhesive tape, and then electrolytic copper foil is removed, obtain the film sample comprising resin layer.Then, according to JIS K7127, by above-mentioned film Sample cuts into defined size, makes evaluation test film.For the test film, tried using Shimadzu Seisakusho Ltd.'s small desk Machine EZ-SX is tested, with 10mm/ minutes measurement stress [MPa] of tensile speed and strain [%].Strain [%] at this time is test segment It is higher can to evaluate bigger toughness, therefore evaluates toughness by the strain [%] for elongation when splitting.

For evaluation criteria, by strain [%] less than 2.0% the case where is set as ×, 2.0% or more situation is set as 〇. Its evaluation result is shown in table 40,41 together.

[working life]

Viscosity after using eastern machine industry system cone plate type viscometer TPE-100-H to measure the dispersion of each composition is as initial stage Viscosity.Later, be put into can be closed container in be placed at a temperature of 23 DEG C, after measurement 48 hours with 96 hours after viscosity And it evaluates.For evaluation criteria, the increment rate of the viscosity after 96 hours is that person is set as 〇 within 30%, by the increase after 48 hours Rate be 30% within person be set as △, by the increment rate after 48 hours be 30% or more person be set as ×.The up time of × person compared with It is short, therefore when a liquid or film-form person are from cryo-conservation to room temperature, if not carrying out next process in early days, it is likely that generate Problem, but the up time of 〇 person is longer, and therefore, a liquid, film-form are easy to be operated.

[table 40]

* 6-1) 50 mass % of heat-curing resin 6-1:Epiclon HP-4032 Dainippon Ink Chemicals solid component Cyclohexanone varnish (cyclic ether compound with naphthalene skeleton)

* 6-2) heat-curing resin 6-2:NC-7300L Nippon Kayaku K. K solid component 50 mass % hexamethylene Ketone varnish (cyclic ether compound with naphthalene skeleton)

* 6-3) heat-curing resin 6-3:YX-8800 Mitsubishi chemical Co., Ltd solid component 50 mass % hexamethylene Ketone varnish (cyclic ether compound with anthracene skeleton)

* 6-4) heat-curing resin 6-4:Epiclon HP-7200 solid component 50 the cyclohexanone varnish of mass % (have The cyclic ether compound of bicyclopentadiene skeleton)

* 6-5) heat-curing resin 6-5:NC-3000H Nippon Kayaku K. K solid component 50 mass % hexamethylene Ketone varnish (cyclic ether compound with biphenyl backbone)

* 6-6) heat-curing resin 6-6:YX-4000 Mitsubishi chemical Co., Ltd solid component 50 mass % hexamethylene Ketone varnish (cyclic ether compound with biphenyl backbone)

* 6-7) heat-curing resin 6-7:Epiclon N-740 Dainippon Ink Chemicals solid component 50 mass % ring Hexanone varnish

* 6-8) 830 Dainippon Ink Chemicals's system of heat-curing resin 6-8:Epiclon

* 6-9) heat-curing resin 6-9:JER827 Mitsubishi chemical Co., Ltd system

* 6-10) phenoxy resin 6-1:YX6954 Mitsubishi chemical Co., Ltd solid component 30 mass % cyclohexanone Varnish

* 6-11) curing agent 6-1:HF-1 is bright and is melted into 60 mass % cyclohexanone varnish of Co. Ltd. system solid component

* 6-12) curing agent 6-2: bisphenol-A diacetate esters Tokyo Chemical Industry Co., Ltd system (active ester)

* 6-13) curing catalysts 6-1:2E4MZ (2-ethyl-4-methylimidazole) Shikoku Chem system

* 6-14) filler 6-1:Adma Fine SO-C2 Co., Ltd.'s Admatechs system (silica)

* 6-15) organic solvent 6-1: dimethylformamide

* 6-16) defoaming agent 6-1:BYK-352BYK Chemie JAPAN Co. Ltd. system

* 6-17) cellulose powder: NP fiber W-06MG (6 μm of average grain diameter) Nippon Paper system

[table 41]

The result as documented by table 40,41 can be determined clearly, by the way that Cellulose nanocrystal particle and fiber is applied in combination Filler other than plain nano-crystalline granule can obtain working life excellent hardening resin composition, can obtain not only often Temperature and even if component installation when high-temperature area and also maintain the various characteristics such as low thermal expansion rate and toughness, heat resistance excellent Solidfied material.Though being able to confirm that by using active ester in addition, table 40, table 41 are not recorded as curing agent, make opposite dielectric Constant and dielectric loss angle tangent reduce.

<the 7th embodiment>

[preparation of fine cellulose fiber]

Production Example 6 (CNF dispersion 1)

By BK bleached kraft pulp fibres (the Fletcher Challenge Canada corporation Machenzie of coniferous tree CSF650ml after) being sufficiently stirred in the ion exchange water of 9900g, TEMPO is successively added relative to pulp quality 100g (ALDRICH corporation 2,2,6,6- tetramethyl piperidine 1- oxygroup free radical) 1.25 mass %, 12.5 mass % of sodium bromide, secondary chlorine Sour 28.4 mass % of sodium.Using pH-stat, 0.5M sodium hydroxide is added dropwise and pH is remained 10.5.Reaction is carried out 120 minutes After (20 DEG C), stop the dropwise addition of sodium hydroxide, obtains oxidation paper pulp.It is using ion exchange water that obtained oxidation paper pulp is sufficiently clear It washes, is then carried out dehydrating.Later, oxidation paper pulp 3.9g and ion exchange water 296.1g is used into high-pressure homogenizer ((Sugino machine corporation, Starburst LabHJP25005) carries out 2 miniaturizations with 245MPa and handles, and is contained The fine cellulose fiber dispersion liquid (1.3 mass % of solid component concentration) of carboxyl.

Then, the carboxylic fine cellulose fiber dispersion liquid 4088.75g of gained is put into beaker, adds ion exchange The aqueous solution of 0.5 mass % is made in water 4085g, is stirred 30 minutes for (25 DEG C) at room temperature with mechanical agitator.Then, 1M is put into Aqueous hydrochloric acid solution 245g reacts it 1 hour.After reaction, reprecipitation is carried out with acetone, filtered, later, used Acetone/ion exchange water is cleaned, and demineralizing acid and salt are removed.It is eventually adding acetone to be filtered, obtains carboxylic fine fibre Acid type cellulose fibre dispersion liquid (5.0 matter of solid component concentration containing acetone for the state that cellulose fiber is swollen in acetone Measure %).It filters, later, is cleaned with ion exchange water after reaction, remove demineralizing acid and salt.Then, it is carried out with acetone molten Agent displacement, obtains the dispersion liquid that solid component is adjusted to 5.0 mass %.Then, it is compounded 830 Dainippon Ink Chemicals of Epiclon Make (bisphenol f type epoxy resin) 250g and JER827 Mitsubishi chemical Co., Ltd system (bisphenol A type epoxy resin) 100g and ELM100 Sumitomo Chemical Company Ltd system (using amine as the epoxy resin of precursor: triglycidyl group amino-phenol) The 250g and dispersion liquid 1000g that solid component is adjusted to 5.0 mass % with the progress solvent displacement of aforementioned acetone, after stirring Acetone is removed with evaporator, obtains acid type cellulose fibre dispersion (avarage fiber diameter 3.3nm, CNF containing epoxy resin 7.7 mass % of concentration).

Production Example 7 (CNF dispersion 2)

By BK bleached kraft pulp fibres (the Fletcher Challenge Canada corporation Machenzie of coniferous tree CSF650ml after) being sufficiently stirred in the ion exchange water of 9900g, TEMPO is successively added relative to pulp quality 100g (ALDRICH corporation 2,2,6,6- tetramethyl piperidine 1- oxygroup free radical) 1.25 mass %, 12.5 mass % of sodium bromide, secondary chlorine Sour 28.4 mass % of sodium.Using pH-stat, 0.5M sodium hydroxide is added dropwise and pH is remained 10.5.Reaction is carried out 120 minutes After (20 DEG C), stop dripping for sodium hydroxide, obtains oxidation paper pulp.It is using ion exchange water that obtained oxidation paper pulp is sufficiently clear It washes, is then carried out dehydrating.Later, oxidation paper pulp 3.9g and ion exchange water 296.1g is used into high-pressure homogenizer ((Sugino machine corporation, Starburst LabHJP25005) carries out 2 miniaturizations with 245MPa and handles, and is contained The fine cellulose fiber dispersion liquid (1.3 mass % of solid component concentration) of carboxyl.

Then, the carboxylic fine cellulose fiber dispersion liquid 4088.75g of gained is put into beaker, adds ion exchange The aqueous solution of 0.5 mass % is made in water 4085g, is stirred 30 minutes for (25 DEG C) at room temperature with mechanical agitator.Then, 1M is put into Aqueous hydrochloric acid solution 245g reacts it 1 hour.After reaction, reprecipitation is carried out with acetone, filtered, later, used Acetone/ion exchange water is cleaned, and demineralizing acid and salt are removed.It is eventually adding acetone to be filtered, obtains carboxylic fine fibre Acid type cellulose fibre dispersion liquid (5.0 matter of solid component concentration containing acetone for the state that cellulose fiber is swollen in acetone Measure %).It filters, is cleaned later with ion exchange water after reaction, remove demineralizing acid and salt.Solvent displacement is carried out with acetone Afterwards, solvent displacement is carried out with DMF, obtains the acid type cellulose containing DMF of the state of carboxylic fine cellulose fiber swelling Fiber dispersion (avarage fiber diameter 3.3nm, 5.0 mass % of solid component concentration).

Acid type cellulose fibre dispersion liquid 400g and hexyl amine 3g by gained containing DMF, which are put into, to be had magnetic stirring apparatus, stirs In the beaker for mixing son, made it dissolve with ethyl alcohol 3000g.Reaction solution is reacted 6 hours under room temperature (25 DEG C).It crosses after reaction Filter, is cleaned with DMF and solvent is replaced, and it is fine thus to obtain the fine cellulose that amine is connect by ionic bond with fine cellulose fiber It ties up complex (5.0 mass % of solid component concentration).Then, it is compounded 830 Dainippon Ink Chemicals's system (Bisphenol F type ring of Epiclon Oxygen resin) 25g and JER827 Mitsubishi chemical Co., Ltd system (bisphenol A type epoxy resin) 10g and ELM100 Sumitomo Chemical Co. Ltd. system (using amine as the epoxy resin of precursor: triglycidyl group amino-phenol) 25g and amine by ionic bond with The fine cellulose fiber complex 200g of aforementioned fine cellulose fiber connection, DMF is removed, obtain after stirring with evaporator Fine cellulose fiber complex (the CNF concentration that amine containing epoxy resin is connect by ionic bond with fine cellulose fiber 15.4 mass %).

The dispersibility of the CNF manufactured with the method for Production Example 7 is especially good, even if special without using high-pressure homogenizer etc. Dispersion machine can also be dispersed using usual way.

Production Example 8 (CNF dispersion 3)

To fine cellulose fiber ((Sugino machine corporation BiNFi-s, avarage fiber diameter 80nm) 10 matter It measures % and carries out dewatering and filtering, the acetone of 10 times of amounts of screening quality is added, stirring is filtered after 30 minutes.It is repeated 3 times displacement behaviour Make, the acetone of 20 times of amounts of screening quality is added, makes fine cellulose fiber dispersion liquid (5.0 matter of solid component concentration Measure %).Then, it is compounded 830 Dainippon Ink Chemicals's system (bisphenol f type epoxy resin) 250g and JER827 Mitsubishi Chemical of Epiclon Co. Ltd. system (bisphenol A type epoxy resin) 100g and ELM100 Sumitomo Chemical Company Ltd system is (using amine as precursor Epoxy resin: triglycidyl group amino-phenol) 250g and aforementioned fine cellulose fiber dispersion liquid 1000g, will after stirring Acetone is removed with evaporator, obtains the cellulose fibre dispersion (7.7 mass % of CNF concentration) containing epoxy resin.

Production Example 9 (CNC dispersion 1)

The scraps of paper of dry coniferous tree bleached kraft pulp are handled with shredding machine and sprayer of hammer crusher, cotton like is made Fiber.The fiber of the cotton like is taken out into 100g with adiabatic drying quality, is suspended in 64% aqueous sulfuric acid 2L, at 45 DEG C Hydrolyze it 45 minutes.

After the filtering of thus obtained suspension, the ion exchange water of 10L is injected, stirring is uniformly dispersed it, obtains Dispersion liquid.Then, it is repeated 3 times the process that dehydration is filtered to the dispersion liquid, obtains dehydration piece.Then, gained is dehydrated piece Be diluted with the ion exchange water of 10L, bit by bit while stirring addition 1N sodium hydrate aqueous solution, make pH 12 or so.Later, dehydration is filtered to the suspension, adds the ion exchange water of 10L, stirring is filtered dehydration, repeats The process 2 times.

Then, ion exchange water is added to gained dehydration piece, prepares 2% suspension.By the suspension with wet type micronized ((Sugino machine corporation " Ultimaizer "), by 10 times, obtains cellulose and receives device under the pressure of 245MPa The brilliant particle aqueous dispersion of rice.

Later, carry out solvent displacement with acetone, obtain the state of Cellulose nanocrystal granules swell acetone dispersion liquor (Gu 5.0 mass % of body constituent concentration).Cellulose nanocrystal particle in gained dispersion liquid is observed and measured with AFM, it is as a result average Crystallization width is 10nm, average crystallite length is 200nm.

Then, it is compounded 830 Dainippon Ink Chemicals's system (bisphenol f type epoxy resin) 50g and JER827 Mitsubishi of Epiclon Co. Ltd. system (bisphenol A type epoxy resin) 20g and ELM100 Sumitomo Chemical Company Ltd system is learned (using amine as precursor Epoxy resin: triglycidyl group amino-phenol) 50g and aforementioned acetone dispersion liquor 200g, by acetone evaporator after stirring Removal, obtains the acid type cellulose fibre dispersion containing epoxy resin.

Production Example 10 (CNC dispersion 2)

Absorbent cotton (white cross Co. Ltd. system) is taken out into 100g with adiabatic drying quality, it is made to be suspended in 64% sulfuric acid water Solution 2L is hydrolyzed 45 minutes in 45 DEG C.

After the filtering of thus obtained suspension, the ion exchange water of 10L is injected, stirring is uniformly dispersed it, obtains Dispersion liquid.Then, it is repeated 3 times the process that dehydration is filtered to the dispersion liquid, obtains dehydration piece.Then, it is handed over the ion of 10L Water is changed by gained dehydration piece dilution, the sodium hydrate aqueous solution of 1N is added bit by bit while stirring, makes pH 12 or so.It Afterwards, by the suspension filtering means dehydration, the ion exchange water of 10L is added, stirring is filtered dehydration, repeats the process 2 times.

Then, ion exchange water is added in obtained dehydration piece, prepares 2% suspension.With wet type micro-granulating device ((Sugino machine corporation " Ultimaizer ") makes the suspension, by 10 times, obtain fiber with the pressure of 245MPa Plain nano-crystalline granule aqueous dispersions.

Later, carry out solvent displacement with acetone, obtain the state of Cellulose nanocrystal granules swell acetone dispersion liquor (Gu 5.0 mass % of body constituent concentration).Cellulose nanocrystal particle in gained dispersion liquid is observed and measured with AFM, it is as a result average Crystallization width is 7nm, average crystallite length is 150nm.

Then, it is compounded 830 Dainippon Ink Chemicals's system (bisphenol f type epoxy resin) 50g and JER827 Mitsubishi of Epiclon Co. Ltd. system (bisphenol A type epoxy resin) 20g and ELM100 Sumitomo Chemical Company Ltd system is learned (using amine as precursor Epoxy resin: triglycidyl group amino-phenol) 50g and aforementioned acetone dispersion liquor 200g, by acetone evaporator after stirring Removal, obtains the acid type cellulose fibre dispersion containing epoxy resin.

According to the record of following table 42,43, after each ingredient is stirred in compounding, the high-pressure homogenizer of the mechanical industrial system of Jitian is used Nanovater NVL-ES008, being repeated 6 times makes its dispersion, prepares each composition.It should be noted that the numerical value in table 42,43 Indicate mass parts.

[exudation on through hole periphery]

In the size of 150mm × 100mm and the FR-4 copper-clad laminated board (copper is 18 μm thick) of thickness 1.6mm, 0.8mm is utilized The drill of diameter is spaced apart the hole at the 30 of 3 column, 10 row with 10mm, according to electroless copper, cathode copper plating sequence into Row processing prepares to implement the test substrate of 25 μm of copper thickness of copper plating on the surface of copper-clad laminated board.By the test After substrate polishing grinding, there is the plate of the opening portion of the circle of 0.9mm diameter using the part in hole, through silk-screen printing into through-hole Each composition is filled, then, after filling, is put into heated air circulation type drying oven, precuring in 1 hour is carried out at 120 DEG C, is tried Test piece.With amplification sem observation test film, the state of the exudation of solidfied material is evaluated.For evaluation criteria, infiltration will not be observed completely It is evaluated as 〇 out, although can be because the dimension enlargement person of plate is evaluated as △, along grinding for polishing by the exudation for not overflowing shape Polishing scratch and the exudation person that the spilling shape of only resin exudation occurs be evaluated as ×.Show the result in table 42,43.

[abrasiveness]

For having rated the test film of the exudation on through hole periphery, abrasiveness is evaluated with polishing grinding (#320).It uses In the observation of magnifying glass, will completely removing solidfied material with 1 time, person is set as 〇, will need 2 times or more persons be set as ×.It shows the result in Table 42,43.

[the expansion trace on through hole]

For having rated the test film of abrasiveness, according to electroless copper (Thru-Cup PEA, upper industrial group, village system), electricity The sequence of solution copper plating (10 μm of copper thickness) is handled.Then, after passing through 3 times in 265 DEG C of peak temperature of reflow ovens, Part on visual valuation hole.By absolutely not expanding trace on 15 through holes, person is set as zero, will observe on 1~5 through hole To expansion trace person be set as △, by 6 or more through holes observe expansion trace person be set as ×.Show the result in table 42,43.

[table 42]

Embodiment 7-1~7-4 includes heat-curing resin 7-1~7-3, therefore embodiment, comparative example in CNF dispersion Resin component it is almost the same.

* 7-1) 830 Dainippon Ink Chemicals's system (bisphenol f type epoxy resin) of heat-curing resin 7-1:Epiclon

* 7-2) heat-curing resin 7-2:jER827 Mitsubishi chemical Co., Ltd system (bisphenol A type epoxy resin)

* 7-3) heat-curing resin 7-3:Sumiepoxy ELM100 Sumitomo Chemical Company Ltd system (makees amine For the epoxy resin of precursor: triglycidyl group amino-phenol)

* 7-4) heat-curing resin 7-4:Denacol EX-212 Nagase ChemteX Co. Ltd. system (1,6 oneself two Alcohol diglycidyl ether)

* 7-5) curing agent 7-1:2MZA-PW Shikoku Chem system (2,4- diamino -6- [2 '-methyl miaows Oxazolyl-(1 ')]-ethyl-s-triazine)

* 7-6) save stabilization agent 7-1:Cureduct L-07N Shikoku Chem system (5 matter of borate Measure the compounding product of % and epoxy resin and novolac resin)

* 7-7) the standby northern dusting Industrial Co., Ltd's system (calcium carbonate) of inorganic filler 7-1:Softon 1800

* 7-8) defoaming agent 7-1:KS-66 Shin-Etsu Chemial Co., Ltd system

[table 43]

The result as documented by table 42,43 can clearly confirm, fine as fine cellulose fiber by using making Powder is scattered in the hardening resin composition of resin filler, and can obtain will not in the heating in component installation Expansion is being generated on the hole of filling perforation and is not generated the exudation of resin component, will not be generated hole portion in grinding process The filling perforation material of recess.

Description of symbols

1,3,8,11 conductive patterns

2 core substrates

1a, 4 interconnecting pieces

5 through-holes

6,9 interlayer insulating films

7,10 via holes

12 solder masks

101 circuit boards

102 substrates

103 plated through hole

104 conductor circuit layers

The precuring object or formal solidification object of 105 hardening resin compositions

106 conductor circuit layers

107 are laminated with the multilayer board of lamination layer on core substrate

108 lamination layers

109 conductor circuit layers

When 110 formation lamination layer, via hole is formed on hole, is filled with the solidfied material of hardening resin composition more Layer printed circuit board

111 via holes filled with the solidfied material of hardening resin composition

The residue of issuable hole peripheral portion in 112 grinding process

The recess of issuable hole portion in 113 grinding process

Claims (18)

1. a kind of hardening resin composition is, characterized by comprising: curable resin, at least one-dimensional fine less than 100nm Filler other than powder and the fine powder.

2. hardening resin composition according to claim 1, wherein the fine powder is fine cellulose powder.

3. hardening resin composition according to claim 1, wherein the fine powder is Cellulose nanocrystal Grain.

4. hardening resin composition according to claim 1, wherein other than the fine powder and the fine powder Mix ratio of the filler in whole fillers is by quality ratio the filler other than fine powder: fine powder=100:(0.04~ 30)。

5. hardening resin composition according to any one of claims 1 to 4, wherein the curable resin includes With at least wantonly a kind of the cyclic ether compound in naphthalene skeleton and anthracene skeleton.

6. hardening resin composition according to any one of claims 1 to 4, wherein the curable resin includes Selected from the group being made of the cyclic ether compound with bicyclopentadiene skeleton and the phenolic resin with bicyclopentadiene skeleton In it is at least one kind of.

7. hardening resin composition according to any one of claims 1 to 4, wherein the curable resin includes Phenoxy resin.

8. hardening resin composition according to any one of claims 1 to 4, wherein the curable resin includes It is at least one kind of in the group being made of the cyclic ether compound with biphenyl backbone and the phenolic resin with biphenyl backbone.

9. a kind of dry film, which is characterized in that there is resin layer, the resin layer is by curable resin described in claim 1 Composition is coated on film and made of drying.

10. a kind of solidfied material, which is characterized in that it is by hardening resin composition described in claim 1 or claim 9 Made of the resin layer solidification of the dry film.

11. a kind of electronic component, which is characterized in that have solidfied material described in any one of claim 10.

12. a kind of hardening resin composition, which is characterized in that it is used to be filled in the recess portion and through hole of printed circuit board At least one, the curability oil/fat composition includes:

(A) at least one-dimensional fine powder less than 100nm and

(B) Thermocurable ingredient.

13. hardening resin composition according to claim 12 is comprising using amine as the cyclic ether chemical combination of precursor (B) Thermocurable ingredient described in object conduct.

14. hardening resin composition according to claim 12 is comprising bisphenol A type epoxy resin and bisphenol-f type (B) Thermocurable ingredient described in epoxy resin conduct.

15. hardening resin composition according to claim 12 is comprising (C) boric acid ester compound.

16. hardening resin composition according to claim 12 is comprising (D) other than (A) fine powder Filler.

17. a kind of solidfied material, which is characterized in that it is to solidify hardening resin composition described in claim 12 's.

18. a kind of printed circuit board, which is characterized in that at least one of recess portion and through hole of printed circuit board are wanted by right The filling of solidfied material described in asking 17.