KR20190127942A - Curable resin composition, dry film, hardened | cured material, electronic component, and printed wiring board - Google Patents

Abstract

Provided is a curable resin composition capable of maintaining a low coefficient of thermal expansion even in a high temperature region at the time of mounting a component and obtaining a cured product excellent in various properties such as toughness, a dry film, a cured product, and an electronic component using the same. It is curable resin composition containing curable resin, the fine powder whose one dimension is smaller than 100 nm, and filler other than fine powder. It is a dry film, hardened | cured material, and an electronic component using this curable resin composition.

Description

Curable resin composition, dry film, hardened | cured material, electronic component, and printed wiring board

This invention relates to curable resin composition, a dry film, hardened | cured material, and an electronic component. Moreover, this invention relates to curable resin composition, hardened | cured material, and a printed wiring board.

Examples of the electronic component include a wiring board, an active component and a passive component fixed to the wiring board. In some wiring boards, conductors are wired to an insulating substrate to connect and fix an active component, a passive component, and the like. When the insulating layer and the conductor layer are multilayered or a flexible insulating substrate is used, depending on the application. The electronic device is an important electronic component. In addition, a wiring board is used also for a semiconductor package, and curable resin composition and dry films for wiring boards are used as an outer layer after wiring boards or semiconductor mounting. Examples of the active component and the passive component include a transistor, a diode, a resistor, a coil, a capacitor, and the like.

In recent years, with the miniaturization of electronic devices, the required characteristics for electronic parts have become strict. Higher density of wiring has been demanded for the wiring board, and low thermal expansion is required for the material of the wiring board in order to secure the reliability of the wiring and the component connecting portion. Active components and passive components also require miniaturization and high integration, and likewise, low thermal expansion is required to secure reliability.

As a method of achieving low thermal expansion, for example, Patent Literature 1 proposes a method of filling an inorganic filler with a resin to obtain a low thermal expansion rate.

Moreover, as a means of achieving the low thermal expansion property of such a material, the method of reinforcing with a cellulose fiber and making it a fiber reinforced composite material is proposed, for example (patent document 2).

In recent years, with the miniaturization of electronic devices, low dielectric properties are required for electronic components to efficiently transmit high frequencies. As a method of achieving the low dielectric property, for example, Nonpatent Document 1 proposes a method of reducing the relative dielectric constant and dielectric loss tangent using an epoxy resin having a dicyclopentadiene skeleton.

In recent years, with higher performance of electronic devices, higher frequencies have been dealt with than ever before, and electronic components are required to transmit high frequencies efficiently. As a characteristic of a high frequency, a skin effect is mentioned. For example, Non-Patent Document 2 explains that as the frequency increases, the electric current only passes near the surface of the conductor.

Moreover, in recent years, in order to respond to the miniaturization and high functionalization of the apparatus provided with a printed wiring board, the further thin and short reduction of a printed wiring board is advanced. Therefore, in the conductor circuit of the printed wiring board, further thinning and reduction of the mounting area are required.

On the other hand, in the manufacturing method of a printed wiring board, after filling a resin filler into recesses and through-holes, such as a via hole and a through hole provided in the wiring board, hardening and grinding | polishing to make a smooth surface, the via hole and through hole which filled these resin fillers In addition, a method of building up an insulating layer and a conductor layer and multiplying the layer is widely employed.

As a resin filler used for such a method, the material excellent in various characteristics, such as filling property into a recessed part and a through hole, abrasiveness of hardened | cured material, and heat resistance, is calculated | required, and the thermosetting resin composition like patent document 3 is proposed.

On the other hand, for the purpose of further densification, in recent years, a method of providing component mounting by arranging wiring such as conductor pads or via holes on recesses or through holes filled with resin fillers and through holes or the like has been adopted.

Japanese Patent Laid-Open No. 2001-72834 Japanese Patent Laid-Open No. 2011-001559 Japanese Patent Publication No. 2015-10146

Network Polymer Vol. 17, No. 2 (1996) pp69 Physics Education Vol. 61, No. 1 (2013) Pages 18 to 20

However, in the material of patent document 1, in order to obtain desired low thermal expansion coefficient, it is necessary to fill an inorganic filler in large quantities, and there existed a problem that the physical property of hardened | cured material, such as toughness, was inferior.

In addition, the inventors of the present invention have found that there is a new problem that the material described in Patent Literature 1 has a large thermal expansion coefficient in the temperature range at the time of component mounting exceeding 200 ° C, which is ineffective for securing reliability.

Then, the 1st objective of this invention is providing the curable resin composition which can maintain the low thermal expansion rate even in the high temperature area | region at the time of component mounting, and can obtain the hardened | cured material excellent in various characteristics, such as toughness.

The 1st other object of this invention is to provide the dry film, hardened | cured material, and electronic component which used the said curable resin composition.

Moreover, according to the material of patent document 2, since the fiber of an average fiber diameter of 4-200 nm is disperse | distributed in a matrix material, the low thermal expansion composite material can be obtained.

However, in the method described in Patent Document 2, cellulose fibers are selected in order to improve the low thermal expansion property, but on the other hand, especially in the case of using an electronic component having a laminated structure for the purpose of miniaturization, high density, and high integration, insulation reliability between layers is particularly high. The inventors found out that there is a new problem of this worsening.

Then, the 2nd object of this invention is providing the curable resin composition which can obtain the hardened | cured material which is excellent in insulation reliability between layers, even when it is made into the electronic component of a laminated structure for the purpose of low thermal expansion, and miniaturization, high density, and high integration. There is.

The 2nd other object of this invention is to provide the dry film, hardened | cured material, and electronic component which used the said curable resin composition.

In addition, in increasing the frequency of electronic components, it is important not only to have a low dielectric property, but also to be able to form a circuit with high accuracy. In this regard, the present inventors found that in the insulating layer described in Non-Patent Document 1, low dielectric properties are obtained, but adhesion strength with a high-precision circuit (plated copper) is not obtained.

Then, the 3rd objective of this invention is providing the curable resin composition which has a low dielectric property and can obtain the hardened | cured material with favorable adhesiveness of hardened | cured material and plated copper.

Moreover, the 3rd other object of this invention is to provide the dry film, hardened | cured material, and electronic component which used the said curable resin composition.

In addition, the said skin effect is expressed also in the wiring of an electronic component, and means that the high frequency passes only the very surface of wiring. Therefore, in order to transmit high frequency efficiently, it is thought to smooth the interface of the wiring of an electronic component and an insulating material.

However, when this smoothing is performed, there exists a problem that the adhesiveness (filling strength) of the plating copper which comprises an insulation material and wiring falls.

On the other hand, in order to improve the adhesiveness of the plating copper which comprises wiring, it is generally performed to remove the smear which generate | occur | produces in the bottom part (desmear) at the time of punching an insulating material with a laser, and to roughen an insulating material surface.

However, when such roughening is performed, a problem arises in that high frequency cannot be transmitted efficiently.

Therefore, the 4th main objective of this invention is curable resin which can remove the smear by laser processing in a desmear process, and can obtain the hardened | cured material which is excellent also in peeling strength while having small surface roughness which is favorable for a high frequency transmission. It is to provide a composition.

Moreover, the 4th other object of this invention is to provide the dry film, hardened | cured material, and electronic component which used the said curable resin composition.

Moreover, according to the material of patent document 2, since the fiber of an average fiber diameter of 4-200 nm is disperse | distributed in a matrix material, the low thermal expansion composite material can be obtained.

However, in the composite material, the present inventors have found that when the plated copper is formed in the solid form on the material, a new problem arises that expansion occurs in the plated copper due to thermal history such as component mounting.

Therefore, the fifth main object of the present invention is low thermal expansion and copper plating is carried out for the purpose of producing a wiring on the cured product of the composition, and the plating copper is formed in a solid state for the purpose of electromagnetic shielding in addition to the wiring pattern. Also in the case, it is providing the curable resin composition which can obtain the hardened | cured material excellent in high temperature resistance which does not generate | occur | produce expansion in plating copper by a thermal history.

A 5th other object of this invention is to provide the dry film, hardened | cured material, and electronic component which used the said curable resin composition.

Moreover, in the material of patent document 1, in order to obtain desired low thermal expansion rate, the inorganic filler must be filled in large quantities, and there existed a problem that the physical property of hardened | cured material, such as toughness, was inferior.

In addition, the inventors of the present invention have found that there is a new problem that the material described in Patent Literature 1 has a large thermal expansion coefficient in the temperature range at the time of component mounting exceeding 200 ° C, which is ineffective for securing reliability.

Accordingly, a sixth object of the present invention is to provide a curable resin composition capable of maintaining a low coefficient of thermal expansion even in a high temperature region at the time of mounting a component and obtaining a cured product excellent in various properties such as toughness and heat resistance.

A 6th other object of this invention is to provide the dry film, hardened | cured material, and electronic component which used the said curable resin composition.

Moreover, when the thermosetting resin composition like patent document 3 is used as a resin filler about the said method used for the manufacturing method of a printed wiring board, the conductor pad, via hole, etc. on recessed parts, such as a via hole and a through hole filled with a resin filler, a through hole, etc. Has a problem that the expansion of the metal wiring in the high temperature heating process at the time of mounting the component affects the reliability.

In addition, the thermosetting resin composition filled in the recess and the through hole (hereinafter also referred to simply as the “hole part”) has a problem of spreading around the hole part and the like during curing because the resin component is melted and cured by heating. there was. Since such a pulverized resin composition is thin in the filler component, it cannot be completely removed by polishing in the next step due to its adhesiveness, and remains, causing a problem of plating.

In addition, in the polishing process after the curing of the thermosetting resin composition filled in the recesses and through holes, it is necessary to completely remove the protruding of the resin fillers around the holes and the like. As a result, the holes or the like may be removed by excessive polishing. Another problem was that the recessed portion did not form a perfect smooth surface.

Then, the 7th main objective of this invention is providing the curable resin composition which can solve the above-mentioned subject, specifically, the via hole, the through hole, etc. which were filled with the resin filler also in the high temperature heating process at the time of component mounting. No expansion occurs in wiring such as conductor pads or via holes on recesses or through holes in the recesses, and in the case of curing, there is no bleeding of the resin composition having a thin filler component, and in the polishing process after curing, excessive polishing for smoothing is performed. It is providing the curable resin composition in which recesses, such as a hole part, do not generate | occur | produce either.

It is another 7th object of this invention to provide the hardened | cured material of curable resin composition which can solve the above-mentioned subject, and the printed wiring board in which the hole part etc. were filled with this hardened | cured material.

As a result of earnestly examining the present inventors, at least one dimension of fillers such as silica, calcium carbonate, barium sulfate, talc, titanium oxide, etc., which are conventionally used as fillers for electronic component materials such as solder resists, interlayer insulating materials, and hole filling materials By using together and mixing fine powder smaller than this 100 nm (henceforth simply called "fine powder"), it discovered that the said subject could be solved unexpectedly, and came to solve this invention.

That is, the curable resin composition of the 1st aspect of this invention is characterized by including curable resin, the fine powder at least one dimension smaller than 100 nm, and fillers other than this fine powder.

In the present invention, as the fine powder, fine cellulose powder (hereinafter simply referred to as "CNF") or cellulose nanocrystal particles (hereinafter simply referred to as "CNC") are used. In addition, the compounding ratio in all the fillers of the said fine powder and fillers other than this fine powder is suitably mass ratio (filler: fine powder other than fine powder) = 100: (0.04-30).

In the present invention, the curable resin includes a cyclic ether compound having at least any one of a naphthalene skeleton and an anthracene skeleton, or a phenol resin having a cyclic ether compound having a dicyclopentadiene skeleton and a dicyclopentadiene skeleton. It is preferable that it contains at least 1 sort (s) chosen from the group which consists of, or it contains a phenoxy resin, or contains at least 1 sort (s) chosen from the group which consists of a cyclic ether compound which has a biphenyl skeleton, and a phenol resin which has a biphenyl skeleton. Do.

The dry film of this invention has a resin layer in which the said curable resin composition is apply | coated and dried on a film, It is characterized by the above-mentioned.

The cured product of the present invention is characterized in that the resin layer of the curable resin composition or the dry film is cured.

The electronic component of this invention is equipped with the said hardened | cured material, It is characterized by the above-mentioned.

In the present invention, the cellulose nanocrystal particles are hydrolyzed cellulose raw materials with a high concentration of inorganic acid (hydrochloric acid, sulfuric acid, hydrobromic acid, etc.) to isolate only the crystalline portion except for the amorphous portion. Specifically, crystals containing no amorphous portion obtained by hydrolysis at a concentration of 60 wt% or more with a strong acid having a high concentration of 7 wt% or more, preferably 9 wt% or more, and more preferably sulfuric acid. to be.

Moreover, the present inventors earnestly examined for the said subject, and as a filling material of recesses and through holes, such as a via hole and a through hole of a printed wiring board, the curable resin composition which disperse | distributed the fine powder and thermosetting component smaller than 100 nm at least one dimension is carried out. By using this, the inventors have newly found that the above-mentioned problem is solved, and have completed the present invention.

The curable resin composition of the 2nd aspect of this invention is a curable resin composition for filling in at least one of the recessed part and the through hole of a printed wiring board, (A) At least one dimension is fine powder smaller than 100 nm, and (B) Thermosetting component It characterized in that it comprises a.

It is preferable that the curable resin composition of this invention contains the cyclic ether compound which makes amines a precursor as a thermosetting component, and also contains bisphenol-A epoxy resin and bisphenol F-type epoxy resin.

It is preferable that curable resin composition of this invention contains the (C) borate ester compound.

It is preferable that the curable composition of this invention contains (D) fillers other than the said (A) fine powder.

The cured product of the present invention is characterized in that the curable resin composition is cured.

The printed wiring board of the present invention is characterized in that at least one of the recess and the through hole of the printed wiring board is filled with the curable resin composition.

In the present invention, the fine powder is not particularly limited in shape, and may be in the form of fibrous, scaly, granular or the like, and the term "at least one dimension is smaller than 100 nm" means any one of one, two and three dimensions. Mean less than 100 nm. For example, in the case of fibrous fine powder, the two-dimensional is smaller than 100 nm and has an expansion to the remaining one dimension. In the case of the flaky fine powder, one side thereof is smaller than 100 nm and the expansion to the remaining two-dimensional. The thing which has a thing is mentioned, In the case of granular fine powder, what is smaller than 100 nm is mentioned even if it is three-dimensional.

In the present invention, the size of one-dimensional, two-dimensional and three-dimensional in the fine powder, the fine powder is SEM (Scanning Electron Microscope), TEM (Transmission Electron Microscope) or AFM (Atomic Force) It can be measured by observing with a microscope (atomic force microscope).

For example, in the case of flaky fine powder, the average value of the thickness which is the smallest one dimension is measured, and this average thickness shall be smaller than 100 nm. Specifically, 12 points of the fine powder which are drawn diagonally on the micrograph and which are in the vicinity and whose thickness is measurable are randomly extracted, and after removing the thickest fine powder and the thinnest fine powder, The thickness is measured, and the average value is assumed to be smaller than 100 nm.

In the case of fibrous fine powder, the average value (hereinafter also referred to simply as "average fiber diameter") of the smallest two-dimensional fiber diameter is measured, and this average fiber diameter shall be smaller than 100 nm. Specifically, a diagonal line of the micrograph is drawn, and 12 points of fine powder in the vicinity thereof are randomly extracted to remove fine powder of the coarse fiber diameter and the finest fiber diameter, and then the remaining fiber diameter of 10 points is determined. It is assumed that the measured and averaged value is smaller than 100 nm.

In the case of granular fine powder, the average value of particle diameters is measured, and this average particle diameter shall be smaller than 100 nm. Specifically, by drawing a line diagonally in the micrograph, and randomly extracting 12 points of fine powder in the vicinity thereof, removing the fine powder of the largest particle size and the smallest particle size, measuring the particle size of the remaining 10 points, It is assumed that the average value is smaller than 100 nm.

In fine powder with expansion to other dimensions such as fibrous or flaky, the expansion is, for example, less than 1000 nm, preferably less than 650 nm, more preferably less than 450 nm. When expansion is less than 1000 nm, the reinforcement effect by the interaction of fine powder can be acquired effectively.

In the present invention, the definition of the fine cellulose powder is also similar to that of the fine powder.

First, according to the present invention, it is possible to provide a curable resin composition capable of maintaining a low coefficient of thermal expansion even in a high temperature region at the time of mounting a component and obtaining a cured product excellent in various properties such as toughness.

Moreover, according to this invention, the dry film, hardened | cured material, and an electronic component using the said curable resin composition can be provided.

Second, according to the present invention, a curable resin composition capable of obtaining a cured product excellent in insulation reliability between layers can be provided even when an electronic component having a laminated structure is provided for the purpose of miniaturization, high density, and high integration. have.

Moreover, according to this invention, the dry film, hardened | cured material, and an electronic component using the said curable resin composition can be provided.

Third, according to the present invention, it is possible to provide a curable resin composition having low dielectric properties and obtaining a cured product having good adhesion between the cured product and the plated copper.

Moreover, according to this invention, the dry film, hardened | cured material, and an electronic component using the said curable resin composition can be provided.

Fourthly, the present invention provides a curable resin composition capable of removing a smear by laser processing in a desmear process, and having a small surface roughness, which is advantageous for high frequency transmission, and which provides a cured product excellent in peel strength. can do.

Moreover, according to this invention, the dry film, hardened | cured material, and an electronic component using the said curable resin composition can be provided.

Fifthly, according to the present invention, even when the copper plating is carried out for the purpose of producing wiring on the cured product of the composition, and the plating copper is formed in the solid state for the purpose of electromagnetic shielding in addition to the wiring pattern, The curable resin composition which can obtain the hardened | cured material which is excellent in high temperature resistance in which expansion copper does not generate | occur | produce by heat history can be provided.

Moreover, according to this invention, the dry film, hardened | cured material, and an electronic component using this curable resin composition can be provided.

Sixth, the present invention can provide a curable resin composition having excellent pot life, while maintaining a low coefficient of thermal expansion even in a high temperature region at the time of mounting a component and obtaining a cured product having excellent properties such as toughness and heat resistance. have.

Moreover, according to this invention, the dry film, hardened | cured material, and an electronic component using the said curable resin composition can be provided.

Seventhly, according to the present invention, in a printed wiring board having at least one of a recess and a through hole, a conductor pad on a recess or through hole, such as a via hole or a through hole, filled with a resin filler also in a high temperature heating step during component mounting. No expansion occurs in wiring such as via holes, via holes, or the like, and at the time of curing, there is no bleeding of the resin composition having a thin filler component, and in the polishing process after curing, no recesses such as holes due to excessive polishing for smoothing occur. Curable resin composition can be provided.

Moreover, according to this invention, the hardened | cured material of curable resin composition which can solve the above-mentioned subject, and the printed wiring board in which the hole part etc. were filled with this hardened | cured material can be provided.

1-1 is a graph showing the relationship between the compounding amount of silica and fine cellulose powder and the coefficient of thermal expansion.
It is a graph which shows the effect of the thermal expansion rate reduction by combined use of fine cellulose powder.
FIG. 1-2-2 is a graph which shows the effect of reducing the coefficient of thermal expansion by combined use of fine cellulose powder.
It is a graph which shows the effect of the elongation rate improvement by combined use of fine cellulose powder.
1-4 is an explanatory diagram showing a test substrate used in Examples.
2-1 is a partial sectional view which shows one structural example of the multilayer printed wiring board which concerns on an example of the electronic component of this invention.
It is explanatory drawing which shows the test board used in the Example.
2-3 is another explanatory diagram showing a test substrate used in Examples.
2-4 is another explanatory diagram which shows the test board used in the Example.
3-1 is a partial sectional view which shows one structural example of the multilayer printed wiring board which concerns on an example of the electronic component of this invention.
3-2 is an explanatory diagram showing a test substrate used in Examples.
4-1 is a partial sectional view which shows one structural example of the multilayer printed wiring board which concerns on an example of the electronic component of this invention.
4-2 is an explanatory diagram showing a test substrate used in Examples.
5-1 is a partial sectional view which shows one structural example of the multilayer printed wiring board which concerns on an example of the electronic component of this invention.
5-2 is an explanatory diagram showing a test substrate used in Examples.
Fig. 6-1 is a graph showing the relationship between the compounding amount of the silica and cellulose nanocrystal particles and the coefficient of thermal expansion.
6-2-1 is a graph showing the effect of reducing the coefficient of thermal expansion by combined use of cellulose nanocrystal particles.
6-2-2 is a graph showing the effect of reducing the coefficient of thermal expansion due to the combination of cellulose nanocrystal particles.
It is a graph which shows the effect of the elongation improvement by the combined use of a cellulose nanocrystal particle.
6-4 is an explanatory diagram showing a test substrate used in Examples.
It is a schematic sectional drawing which shows an example of the manufacturing method of the printed wiring board using the curable resin composition of this invention.
7-2 is a partial cross-sectional view showing one configuration example of a multilayer printed wiring board according to one example of the printed wiring board of the present invention.
7-3 is a partial sectional view which shows an example of a structure of a multilayer printed wiring board which concerns on an example of the printed wiring board of this invention.
It is a schematic sectional drawing explaining recessed parts, such as a hole part which arises in a grinding | polishing process.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

<< 1st aspect of this invention >>

The curable resin composition of the 1st aspect of this invention has the largest characteristic in the point which used fine powder and fillers other than fine powder together as a filler.

By setting it as such a structure, the hardened | cured material which can maintain low thermal expansion coefficient in the temperature range at the time of component mounting exceeding 200 degreeC, and is excellent in various characteristics, such as toughness, can be provided with respect to a 1st objective.

[Fine powder]

The fine powder to be used in the present invention is a powder having at least one dimension smaller than 100 nm, as described above, not only being close to a fine spherical shape, but also having a fiber shape smaller than 100 nm in cross section and having a sheet shape smaller than 100 nm in thickness ( A scale) etc. are included. Such fine powder has a much larger surface area per unit mass and an increase in the proportion of atoms exposed on the surface, as compared with all three dimensions having 100 nm or more. Therefore, it is thought that the reinforcing effect is expressed by taking an interaction in which the fine powders attract each other, and the thermal expandability is lowered.

The fine powder may be particles having at least one dimension smaller than 100 nm, and the material is not particularly limited, and two or more kinds thereof may be used in combination. As the fine powder, for example, carbon-based, silver, gold, iron, nickel, titanium oxide, cerium oxide, zinc oxide, silica, aluminum hydroxide, etc., such as graphite, graphene, fullerene, single layer carbon nanotubes, and multilayer carbon nanotubes Minerals such as inorganic, clay, smectite, bentonite, fine cellulose powder which opened fiber of plant, and cellulose nanocrystal particles which isolated only crystal part from cellulose raw material, fine chitin obtained by chitin obtained from crustaceans, these fine chitin The polymer system, such as the fine chitosan which carried out more alkali treatment, is mentioned, You may process these to a nanotube, a nanowire, a nanosheet form, and may use 2 or more types together. Among these, as hydrophilic fine powder, metal oxide microparticles | fine-particles, such as titanium oxide, metal hydroxide microparticles | fine-particles, such as aluminum hydroxide, mineral type microparticles | fine-particles, such as clay, fine cellulose fiber, fine chitin, etc. are mentioned. Among these fine powders, in particular, from the viewpoint of the reinforcing effect and the ease of handling, and from the viewpoint of the effect of improving the adhesion to the plated copper and the ease of handling, the fine cellulose powder is preferable. Also preferred are cellulose nanocrystal particles.

The inventors have focused on the fine cellulose powder as a powder having at least one dimension smaller than 100 nm, and have studied intensively the relationship between the blending amount and the thermal expansion rate in comparison with silica, and according to the fine cellulose powder, the reduction in the remarkable thermal expansion rate with a small amount of the compounding powder It was newly found that the effect was obtained (see FIG. 1-1).

In addition, the inventors pay attention to the fact that the compounding of the fine cellulose powder provides a sufficient effect of reducing the coefficient of thermal expansion even with a small amount of compounding. As a result of intensive studies, the inventors have found various characteristics required for insulating materials such as toughness. It was found out that the effect peculiar to the present invention described above can be obtained by using the fine cellulose powder in combination while blending fillers such as silica for securing (see FIGS. 1-2 and 1-3).

When using hydrophilic fine powder as above-mentioned fine powder, it is preferable to hydrophobize the particle | grains, to surface-treat etc. using a coupling agent. Such a treatment can use a known conventional method suitable for fine powder.

The compounding quantity of the fine powder in this invention is 0.04-64 mass% suitably with respect to the total amount of the composition except a solvent, More preferably, it is 0.08-30 mass%, More preferably, it is 0.1-10 mass%. When the compounding quantity of fine powder is 0.04 mass% or more, the effect of reducing a linear expansion coefficient can be obtained favorably, and the effect of improving adhesiveness with plated copper can be obtained favorably. On the other hand, when it is 64 mass% or less, film forming property improves.

Although the fine cellulose powder can be obtained as follows in the fine powder which concerns on this invention, it is not limited to these.

(Fine cellulose powder)

As raw materials of the fine cellulose powder, pulp obtained from natural plant fiber raw materials such as wood, hemp, bamboo, cotton, jute, kenaf, beet, agricultural residues, and cloth, regenerated cellulose fibers such as rayon and cellophane, etc. can be used. Among them, pulp is particularly suitable. Examples of the pulp include chemical pulp, semichemical pulp, chemical pulp, chemical pulp, chemical mechanical pulp, and chemical mechanical pulp, such as kraft pulp and sulfite pulp obtained by pulping a plant raw material chemically or mechanically or in combination of both. , Refiner mechanical pulp, groundwood pulp, and deinking gripping pulp mainly containing these plant fibers, magazine gripping pulp, corrugated gripping pulp and the like can be used. Among them, various kraft pulp derived from conifers having a strong fiber strength, for example, conifer unbleached kraft pulp, conifer oxygen exposed unbleached kraft pulp, and conifer bleached kraft pulp are particularly suitable.

The said raw material mainly consists of cellulose, hemicellulose, and lignin, and content of the lignin is about 0-40 mass% normally, especially about 0-10 mass%. About these raw materials, lignin removal or bleaching process can be performed as needed, and the lignin amount can be adjusted. In addition, the measurement of lignin content can be performed by the Klason method.

Among the cell walls of plants, cellulose molecules are not monomolecules but aggregated regularly to form microfibrils (fine cellulose fibers) having crystallinity which is gathered dozens, which is the basic skeleton material of plants. Therefore, in order to produce fine cellulose powder from the raw materials, the raw materials may be subjected to beating or pulverization treatment, high temperature and high pressure steam treatment, treatment with phosphate or the like, treatment of oxidizing cellulose fibers using N-oxyl compound as an oxidation catalyst, or the like. By carrying out, the method of unwinding the fiber to nano size can be used.

The above-mentioned beating-crushing process is a method of obtaining fine cellulose powder by applying a force directly to raw materials, such as said pulp, mechanically beating-pulverizing, and unwinding a fiber. More specifically, for example, a cellulose fiber obtained by mechanically treating a pulp or the like with a high pressure homogenizer or the like and having a fiber diameter of about 0.1 to 10 μm is used as an aqueous suspension of about 0.1 to 3% by mass, and this is also a grinder or the like. The fine cellulose powder having a fiber diameter of about 10 to 100 nm can be obtained by repeating the grinding to the fusion treatment.

The said grinding | pulverization thru | or crushing process can be performed using grinder "pure fine mill" made from Kurita Kikai Seisakusho etc., for example. This grinder is a millstone grinder that grinds the raw material into ultra-fine particles by the impact, centrifugal force and shear force generated when the raw material passes through the gap between two upper and lower grinders, and is characterized by shearing, grinding, atomization, dispersion, emulsification and fibril. You can be angry at the same time. In addition, the said grinding | pulverization thru | or fusion | melting process can also be performed using the ultrafine grinding | pulverization machine "super mass collider" made by Masyuki Sankyo Co., Ltd. The super mass collider is a crusher that enables ultra-fine granulation to feel as if it melts beyond the area of crushing. The super mass collider is a millstone type ultra-fine grinding machine composed of two upper and lower inorganic ball grindstones which can be adjusted freely. The upper grindstone is fixed, and the lower grindstone rotates at high speed. The raw materials put into the hopper are sent to the gap between the upper and lower grindstones by centrifugal force, and the raw materials are gradually crushed into ultra-fine particles by the strong compression, shear and rolling friction generated therein.

Moreover, the said high temperature high pressure steam process is a method of obtaining fine cellulose powder by unwinding a fiber by exposing raw materials, such as said pulp, to high temperature high pressure steam.

The treatment with phosphate or the like is a treatment method in which the surface of raw materials such as pulp is phosphated to weaken the bonding force between cellulose fibers, and then the refiner is used to release the fibers to obtain fine cellulose powder. For example, the raw material such as the pulp is immersed in a solution containing 50% by mass of urea and 32% by mass of phosphoric acid, and the solution is sufficiently infiltrated between cellulose fibers at 60 ° C, and then heated at 180 ° C to phosphorylate. After advancing and washing this with water, it hydrolyzes at 60 degreeC for 2 hours in 3 mass% hydrochloric acid aqueous solution, washes with water again, and after that in a 3 mass% sodium carbonate aqueous solution about 20 minutes at room temperature Phosphorylation is completed by processing, and fine cellulose powder can be obtained by dissolving this processed material with a refiner.

And the process which oxidizes cellulose fiber using the said N-oxyl compound as an oxidation catalyst is a method of obtaining fine cellulose powder by making it refine | miniaturize after oxidizing raw materials, such as the said pulp.

First, an aqueous dispersion is produced by dispersing natural cellulose fibers in water of about 10 to 1000 times (mass basis) on an absolute dry basis using a mixer or the like. As a natural cellulose fiber used as a raw material of the said fine cellulose fiber, For example, wood pulp, such as a coniferous pulp and a hardwood pulp, non-wood pulp, such as a barley pulp and bagas pulp, a cotton pulp, such as cotton lint and cotton lint, Bacterial cellulose; and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type as appropriate. In addition, in order to enlarge surface area, these natural cellulose fibers may be previously processed, such as beating.

Next, in the aqueous dispersion, an N-oxyl compound is used as an oxidation catalyst to oxidize natural cellulose fibers. As such an N-oxyl compound, for example, 4-carboxy-TEMPO, 4-acetamide-TEMPO, 4-amino-TEMPO, in addition to TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) , 4-dimethylamino-TEMPO, 4-phosphonooxy-TEMPO, 4-hydroxyTEMPO, 4-oxyTEMPO, 4-methoxyTEMPO, 4- (2-bromoacetamide) -TEMPO, 2-azaa However, TEMPO derivatives having various functional groups at the C4 position such as tan N-oxyl and the like can be used. As addition amount of these N-oxyl compounds, a catalytic amount is enough and it can be normally made into the range which becomes 0.1 to 10 mass% on an absolute dry basis with respect to a natural cellulose fiber.

In the oxidation process of the said natural cellulose fiber, an oxidizing agent and a co-oxidant are used together. As the oxidizing agent, for example, ahalogenic acid, hypohalogenic acid and perhalogenic acid and salts thereof, hydrogen peroxide and perorganic acid are mentioned. Among them, alkali metal hypohalogenates such as sodium hypochlorite and sodium hypobromite are suitable. Do. As the co-oxidant, for example, an alkali metal bromide such as sodium bromide can be used. The amount of the oxidizing agent is usually in a range of about 1 to 100% by mass on the basis of absolute drying relative to the natural cellulose fibers, and the amount of the cooxidant is usually about 1 to 30% by mass on an absolute drying basis relative to the natural cellulose fibers. It is a range.

During the oxidation treatment of the natural cellulose fiber, it is preferable to maintain the pH of the aqueous dispersion in the range of 9 to 12 from the viewpoint of promoting the oxidation reaction efficiently. In addition, the temperature of the aqueous dispersion liquid at the time of an oxidation process can be arbitrarily set in the range of 1-50 degreeC, and can react even at room temperature, without temperature control. As reaction time, it can be set as the range for 1 to 240 minutes. Moreover, in order to infiltrate a chemical | medical agent to the inside of a natural cellulose fiber, and to introduce more carboxyl groups into a fiber surface, you may add a penetrant to an aqueous dispersion. Examples of the penetrant include anionic surfactants such as carboxylates, sulfate ester salts, sulfonates, and phosphate ester salts, and nonionic surfactants such as polyethylene glycol and polyhydric alcohols.

After the oxidation treatment of the natural cellulose fibers, it is preferable to perform a purification treatment to remove impurities such as unreacted oxidizers and various by-products contained in the aqueous dispersion prior to miniaturization. Specifically, for example, a method of repeatedly washing with water and filtering oxidized natural cellulose fibers can be used. Although the natural cellulose fiber obtained after a refinement | purification process is used for refinement | miniaturization process in the state impregnated with a suitable amount of water normally, you may make a fibrous form or powder form by performing a drying process as needed.

Next, the refinement | purification of a natural cellulose process is performed in the state disperse | distributed the refined natural cellulose fiber in solvents, such as water. As a solvent as the dispersion medium used in the micronization treatment, water is usually preferred, but alcohols (methanol, ethanol, isopropanol, isobutanol, sec-butanol, tert-butanol, methylcellosolve, ethylcellosolve, etc.) may be used depending on the purpose. , Ethylene glycol, glycerin, etc.), ethers (ethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, etc.), ketones (acetone, methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethyl Soluble organic solvent may be used for water, such as acetamide, dimethyl sulfoxide, etc., and these mixture can also be used. Solid content concentration of the natural cellulose fiber in the dispersion liquid of these solvent suitably sets it as 50 mass% or less. If the solid content concentration of the natural cellulose fiber exceeds 50 mass%, since very high energy is required for dispersion | distribution, it is unpreferable. The refinement of the natural cellulose treatment is the dispersion of low pressure homogenizers, high pressure homogenizers, grinders, cutter mills, ball mills, jet mills, quenchers, cutters, single screw extruders, twin screw extruders, ultrasonic stirrers, home juicer mixers, etc. This can be done using an apparatus.

The fine cellulose powder obtained by a refinement | miniaturization process can be made into the suspension form which adjusted solid content concentration, or the dried powder form according to the objective. Here, in the case of making a suspension form, only water may be used as a dispersion medium, and other organic solvents, such as alcohol, such as ethanol, and mixed solvents, such as surfactant, an acid, and a base, may be used.

By the oxidation treatment and the refinement treatment of the natural cellulose fiber, the hydroxyl group at the C6 position of the structural unit of the cellulose molecule is selectively oxidized via a aldehyde group, and the cellulose group contains a cellulose molecule having a content of 0.1 to 3 mmol / g. The highly crystalline fine cellulose powder having the predetermined number average fiber diameter can be obtained. This highly crystalline fine cellulose powder has a cellulose I-type crystal structure. This means that such fine cellulose powder is surface-oxidized and refine | miniaturized the cellulose molecule derived from nature which has an I-form crystal structure. In other words, the natural cellulose fiber has a multiplicity of fine fibers called microfibrils produced in the course of its biosynthesis to form a higher solid structure, and has a strong cohesive force between the microfibrils (hydrogen between surfaces). Bond) is weakened by the introduction of an aldehyde group or a carboxyl group by an oxidation treatment, and further subjected to a micronization treatment to obtain fine cellulose powder. By adjusting the conditions of the oxidation treatment, the content of the carboxyl group can be increased or decreased to change the polarity, or the average fiber diameter, average fiber length, average aspect ratio, etc. of the fine cellulose powder can be controlled by electrostatic repulsion or miniaturization treatment of the carboxyl group. have.

The natural cellulose fibers having an I-type crystal structure show peaks typical at two positions near 2θ = 14 to 17 ° and around 2θ = 22 to 23 ° in a diffraction profile obtained by measurement of the wide-angle X-ray diffraction image. It can be identified in that it has. The introduction of a carboxyl group into the cellulose molecules of the fine cellulose powder can be confirmed by the presence of absorption (near 1608 cm ⁻¹ ) attributable to a carbonyl group in the total reflection type infrared spectral spectrum (ATR) in the sample from which water is completely removed. have. In the case of a carboxyl group (COOH), absorption exists in 1730 cm <^-1> in said measurement.

In addition, since halogen atoms are attached or bonded to the natural cellulose fibers after the oxidation treatment, dehalogenation treatment may be performed for the purpose of removing such residual halogen atoms. A dehalogenation process can be performed by immersing the natural cellulose fiber after an oxidation process in a hydrogen peroxide solution or an ozone solution.

Specifically, for example, the natural cellulose fiber after the oxidation treatment is in a hydrogen peroxide solution having a concentration of 0.1 to 100 g / L in a bath ratio of about 1: 5 to 1: 100, preferably about 1:10 to 1:60 (mass ratio). Immerse in the condition of. The concentration of the hydrogen peroxide solution in this case is preferably 1 to 50 g / L, more preferably 5 to 20 g / L. The pH of the hydrogen peroxide solution is suitably 8 to 11, more preferably 9.5 to 10.7.

In addition, the quantity [mmol / g] of the carboxyl group in cellulose with respect to the mass of the fine cellulose powder contained in aqueous dispersion can be evaluated by the following method. That is, 60 ml of 0.5-1 mass% aqueous dispersion of the fine cellulose powder sample which dry weight was previously prescribed | regulated, pH was made to about 2.5 with 0.1 M hydrochloric acid aqueous solution, and 0.05 M sodium hydroxide aqueous solution had a pH of about Drop until 11 is obtained and measure the electrical conductivity. From the amount of sodium hydroxide (V) consumed in the neutralization step of the weak acid with a slight change in electrical conductivity, the functional group amount can be determined using the following formula. This functional group amount shows the quantity of a carboxyl group.

Functional amount [mmol / g] = V [ml] × 0.05 / fine cellulose powder sample [g]

In addition, the fine cellulose powder to be used in the present invention may be chemically modified and / or physically modified to increase its functionality. Here, as the chemical formula, functional groups may be added by acetalization, acetylation, cyanoethylation, etherification, isocyanation, etc., or inorganic matters such as silicate or titanate may be complexed or coated by chemical reaction, sol-gel method or the like. It can be carried out by a method such as. As a method of chemical modification, the method of immersing and heating the fine cellulose powder shape | molded in the sheet form in acetic anhydride, for example is mentioned. Moreover, the fine cellulose powder obtained by the process which oxidizes a cellulose fiber using an N-oxyl compound as an oxidation catalyst can mention the method of modifying an amine compound, a quaternary ammonium compound, etc. by the carboxyl group in a molecule | numerator with an ionic bond or an amide bond. have.

As a method of the physical formula, for example, a metal or a ceramic raw material is formed by a physical vapor deposition method (PVD method) such as vacuum deposition, ion plating, sputtering, chemical vapor deposition method (CVD method), plating method such as electroless plating or electrolytic plating, or the like. And a method of coating. These formulas may be before or after the treatment.

In the case of a fibrous form, the fine cellulose powder used for this invention has an average fiber diameter of 3 nm or more, and it is preferable that it is smaller than 100 nm. Since the minimum diameter of the fine cellulose fiber short fibers is 3 nm, less than 3 nm cannot be produced substantially. Moreover, when smaller than 100 nm, the desired effect of this invention is acquired even if it does not add excessively, and film forming property also becomes favorable. In addition, the average fiber diameter of a fine cellulose powder can be measured in accordance with the measuring method of the magnitude | size of the fine powder mentioned above.

(Cellulose Nanocrystal Particles)

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining on the crystalline form of the fine cellulose powder, according to the cellulose nanocrystal particle which hydrolyzed the cellulose raw material and isolate | excluding only the crystalline part except an amorphous part, while surprisingly solving the said subject, It was found that the pot life can also be provided with an excellent curable resin composition.

As a filler, by using together cellulose nanocrystal particles which isolate | separated only the crystal part from the cellulose raw material, and fillers other than this cellulose nanocrystal particle, while maintaining low thermal expansion coefficient in the temperature range at the time of component mounting exceeding 200 degreeC, The curable resin composition excellent in the usable time which can obtain the hardened | cured material excellent in various characteristics, such as heat resistance, can be provided.

By the way, the inventors pay attention to the cellulose nanocrystal particle which isolate | separated only the crystal part only from the cellulose raw material, and compared the silica with the relationship of the compounding quantity and thermal expansion rate, and earnestly examined, According to this cellulose nanocrystal particle, with the small amount of compounding quantity It was found that a significant effect of reducing the coefficient of thermal expansion was obtained (see Fig. 6-1).

Moreover, the inventors mix | blend the said cellulose nanocrystal particle | grains together and mix | blending while compounding the fillers, such as a silica, for ensuring the various characteristic calculated | required for the insulating material of electronic components, such as toughness and heat resistance, and the effect peculiar to this invention It was found that it can be obtained (see Figs. 6-2 and 6-3).

Furthermore, the inventors have found out that according to the cellulose nanocrystal particle containing only a crystalline part, the curable resin composition excellent in the usable time can be provided and exhibits the unique effect which the fine cellulose powder containing an amorphous part does not have.

In the present invention, any of the cellulose nanocrystal particles may be used as long as the cellulose raw material is hydrolyzed with a high concentration of inorganic acid (hydrochloric acid, sulfuric acid, hydrobromic acid, etc.) to isolate only the crystalline portion except for the amorphous portion. The particle size is preferably 3 to 70 nm in average crystal width and 100 to 500 nm in average crystal length, more preferably 3 to 50 nm in average crystal width and 100 to 400 nm in average crystal length, and more preferably. Is 3 to 10 nm in average crystal width and 100 to 300 nm in average crystal length. Here, the crystal width refers to the length of the short side of the particle, and the crystal length refers to the length of the long side of the particle. Such cellulose nanocrystal particles have a much larger surface area per unit mass than those having a larger width and length than this, and increase the proportion of atoms exposed on the surface. Therefore, it is thought that the reinforcing effect is expressed by taking an interaction in which the cellulose nanocrystal particles attract each other, and the thermal expandability is lowered.

Here, the size (average crystal width, average crystal length) of the cellulose nanocrystal particles may be SEM (Scanning Electron Microscope), TEM (Transmission Electron Microscope) or AFM (Atomic Force Microscope) Force microscope) and the like.

Specifically, a line is drawn diagonally on the micrograph, and randomly extracts 12 points of particles that are in the vicinity and can be measured in size at random, and removes the largest and smallest particles, and then removes the size of the remaining 10 points ( Crystal width, crystal length), and each average value is the average crystal width and average crystal length of the cellulose nanocrystal particles.

As cellulose nanocrystal particle | grains, you may use together 2 or more types from which raw material cellulose differs.

It is preferable that such a cellulose nanocrystal particle performs hydrophobization treatment, the surface treatment using a coupling agent, etc. Such a treatment can use a known conventional method suitable for cellulose nanocrystal particles.

The compounding quantity of the cellulose nanocrystal particle in this invention is 0.04-30 mass% with respect to the total amount of the composition except a solvent, More preferably, it is 0.08-20 mass%, More preferably, it is 0.1-10 mass%. to be. When the compounding quantity of cellulose nanocrystal particle | grains is 0.04 mass% or more, the effect of reducing the thermal expansion coefficient can be obtained favorably. On the other hand, when it is 30 mass% or less, film forming property improves.

The cellulose nanocrystal particles according to the present invention can be obtained by hydrolyzing a cellulose raw material with a high concentration of inorganic acid (hydrochloric acid, sulfuric acid, hydrobromic acid, etc.) and isolating only crystal parts except for amorphous parts.

Here, the cellulose raw material includes, but is not particularly limited to, pulp for paper, cotton pulp such as cotton linter or cotton lint, hemp, barley, non-wood pulp such as vargas, cellulose isolated from sea urchin and seaweed, and the like. . Among them, paper pulp is preferable in view of ease of acquisition, and cotton and sea urchin are preferable in that CNC can be produced more excellent in heat resistance.

Examples of paper pulp include hardwood kraft pulp, softwood kraft pulp, and the like.

Examples of the hardwood kraft pulp include bleached kraft pulp (LBKP), unbleached kraft pulp (LUKP), oxygen bleached kraft pulp (LOKP), and the like.

As coniferous kraft pulp, bleached kraft pulp (NBKP), unbleached kraft pulp (NUKP), oxygen bleached kraft pulp (NOKP), etc. are mentioned.

In addition, chemical pulp, semichemical pulp, mechanical pulp, non-wood pulp, degreasing pulp using phage as a raw material, and the like can be given. Examples of the chemical pulp include sulfite pulp (SP), soda pulp (AP), and the like. Semichemical pulp includes semichemical pulp (SCP), chemical groundwood pulp (CGP), and the like. Examples of mechanical pulp include groundwood pulp (GP) and thermomechanical pulp (TMP, BCTMP). As the non-wood pulp, there are ones that are used as raw materials, such as mulberry, cedar mulberry, hemp and kenaf.

These cellulose raw materials may be used individually by 1 type, and may be used in mixture of 2 or more types. In addition, the cellulose nanofibers (hereinafter, simply referred to as "CNF") manufactured by the mechanical digestion method, the phosphate esterification method, the TEMPO oxidation method, etc. may be used as a cellulose raw material.

Subsequently, hydrolysis of the cellulose raw material as described above may be carried out by treating the aqueous suspension or slurry containing the cellulose raw material with sulfuric acid, hydrochloric acid, hydrobromic acid, or the like, or the cellulose raw material in an aqueous solution such as sulfuric acid, hydrochloric acid, hydrobromic acid or the like as it is. It can be performed by suspending. In particular, when pulp is used as a cellulose raw material, it is preferable to use a cutter mill, a pin mill, or the like to form a planar fiber, and then perform hydrolysis treatment in that a uniform hydrolysis treatment can be performed.

In such a hydrolysis process, although temperature conditions are not specifically limited, For example, it can be 25-90 degreeC. Moreover, the conditions of the hydrolysis treatment time are not specifically limited, either, For example, it can be set as 10 to 120 minutes.

In addition, about the cellulose nanocrystal particle obtained by hydrolyzing a cellulose raw material in this way, neutralization treatment can be performed using alkali, such as sodium hydroxide, for example.

Thus, the cellulose nanocrystal particle obtained can be atomized as needed. In this atomization process, a processing apparatus and a processing method are not specifically limited.

As an atomizing apparatus, for example, a grinder (mill grinder), a high pressure homogenizer, an ultra high pressure homogenizer, a high pressure impact grinder, a ball mill, a bead mill, a disk type refiner, a conical refiner, a twin-shaft kneader, vibration Mills, homomixers, ultrasonic dispersers, beaters and the like under high speed rotation can be used.

At the time of an atomization process, although it is preferable to dilute a cellulose nanocrystal particle in water or an organic solvent individually or in combination, it is not specifically limited. Preferred organic solvents include alcohols, ketones, ethers, dimethyl sulfoxide (DMSO), dimethylformamide (DMF) or dimethylacetamide (DMAc). 1 type may be sufficient as a dispersion medium, and 2 or more types may be sufficient as it. Moreover, you may contain solid content other than cellulose nanocrystal particle | grains, for example, a urea with hydrogen bondability, etc. in a dispersion medium.

In addition, the cellulose nanocrystal particles used in the present invention may be chemically modified and / or physically modified to increase the functionality. Here, as the chemical formula, functional groups may be added by acetalization, acetylation, cyanoethylation, etherification, isocyanation, etc., or inorganic matters such as silicate or titanate may be complexed or coated by chemical reaction, sol-gel method or the like. It can be carried out by a method such as. As a physical formula, it can carry out by plating or vapor deposition.

[Filler other than fine powder]

The resin composition of this invention further contains fillers other than the above-mentioned fine powder. Examples of such fillers include inorganic materials such as barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, and titanium oxide. A filler is mentioned. Moreover, when a fine powder is cellulose nanocrystal particle | grains, an organic filler may be sufficient, a cellulose nanofiber may be used as an organic filler, and a silica is preferable among fillers.

It is preferable that it is 3 micrometers or less, and, as for the average particle diameter of this filler, 1 micrometer or less is more preferable. In addition, the average particle diameter of a filler can be calculated | required by the laser diffraction type particle diameter distribution measuring apparatus.

The compounding quantity of this filler is 1-90 mass% in the total amount of the composition except a solvent, Preferably it is 2-80 mass%, More preferably, it is 5-75 mass%. By carrying out the compounding quantity of a filler in the said range, the coating film performance of the hardened | cured material after hardening can be ensured favorably.

The blending ratio in the fillers other than the fine powder and the total filler in the fine powder is (mass: filler other than the fine powder: fine powder) = 100: (0.04 to 30), preferably 100: (0.1 to 20), more preferably Is 100: (0.2 to 10). By using a filler at such a compounding ratio, various characteristics, such as toughness and heat resistance, which are required for the insulating material of an electronic component can be compatible, maintaining a low thermal expansion coefficient.

In addition, it is preferable to make the total amount of the filler mix | blended in curable resin composition into the well-known amount suitably tolerated according to the use characteristic of curable resin composition, for example, the required characteristic of insulating materials, such as the interlayer insulation material of an electronic component. .

<Other blended components except fillers other than fine powder and fine powder according to the first and sixth objects>

In the 1st aspect of this invention, as another compounding component except the fine powder which concerns on 1st and 6th objects, and filler other than fine powder, it is as follows.

Curable Resin

In this invention, it is not specifically limited as curable resin, A well-known thing can be used, For example, although the material containing any 1 type of a thermosetting component and a photocurable component may be sufficient, The material containing a thermosetting component is preferable.

As a thermosetting component, what is necessary is just resin which hardens | cures by heating and shows electrical insulation, For example, the compound which has cyclic ether groups, such as an epoxy compound and an oxetane compound, melamine resin, a silicone resin, benzoguanamine resin, a melamine derivative, and benzoguar Amino resins such as namin derivatives, polyisocyanate compounds, block isocyanate compounds, cyclocarbonate compounds, episulfide resins, bismaleimides, carbodiimide resins, polyimide resins, polyamideimide resins, polyphenylene ether resins, polyphenyls Known thermosetting resins, such as ren sulfide resin, can be used. In particular, a thermosetting resin having at least any one of a plurality of cyclic ether groups and cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in the molecule is preferable. Especially, an epoxy compound and an oxetane compound are preferable and the epoxy resin which is an epoxy compound is more preferable.

Examples of the epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol E type epoxy resins, bisphenol M type epoxy resins, bisphenol P type epoxy resins, and bisphenol Z type epoxy resins. Novolak-type epoxy resins, such as bisphenol-type epoxy resin, bisphenol-A novolak-type epoxy resin, phenol novolak-type epoxy resin, and cresol novolak epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, and arylalkylene type Epoxy resin, tetraphenylolethane type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy Resin, glycidyl methacrylate copolymer type epoxy resin, cyclohexyl maleimide and article Copolymerized epoxy resin of cyl methacrylate, polybutadiene rubber derivative of epoxy modification, CTBN modified epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4 ' Diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris (2,3-epoxypropyl) isocyanur The rate, triglycidyl tris (2-hydroxyethyl) isocyanurate, a phenoxy resin, etc. are mentioned.

Especially, using at least any one of solid epoxy resin solid at 40 degreeC, and semi-solid epoxy resin solid at 20 degreeC, and liquid at 40 degreeC, and using liquid epoxy resin liquid at 20 degreeC is used of this invention. While maintaining the effect, it is also preferable in view of excellent crack resistance during the cold heat cycle. As an example of a solid epoxy resin, semi-solid epoxy resin, and a liquid epoxy resin, the thing of Unexamined-Japanese-Patent No. 2015-10232 is mentioned.

The said thermosetting component is used with a hardening | curing agent as needed. Examples of the curing agent include a phenol resin, a polycarboxylic acid and its acid anhydride, a cyanate ester resin, an active ester resin capped with an acetylation group, a cycloolefin polymer having a carboxyl group, a hydroxyl group, and an active ester structure in the side chain, and the aforementioned compounds. The hardening | curing agent which has a substituent which reacts with a hydroxyl group, a carboxyl group, and a cyclic ether group which has an active ester structure can be mentioned to a part of curable resin, It can be used individually or in combination of 2 or more types.

As said phenol resin, a phenol novolak resin, an alkyl phenol novolak resin, a bisphenol A novolak resin, a dicyclopentadiene type phenol resin, a xylox phenol resin, a terpene modified phenol resin, a cresol / naphthol resin, a polyvinyl phenol, a phenol Conventionally well-known things, such as / naphthol resin, (alpha)-naphthol frame | skeleton containing phenol resin, and triazine containing cresol novolak resin, can be used.

The said polycarboxylic acid and its acid anhydride are the compound which has two or more carboxyl groups in 1 molecule, and its acid anhydride, for example, the copolymer of (meth) acrylic acid, the copolymer of maleic anhydride, and the condensate of dibasic acid. In addition to these, resin which has carboxylic acid terminal, such as carboxylic acid terminal imide resin, is mentioned.

The cyanate ester resin is a compound having two or more cyanate ester groups (-OCN) in one molecule. As the cyanate ester resin, all conventionally known ones can be used. As cyanate ester resin, a phenol novolak-type cyanate ester resin, an alkylphenol novolak-type cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol-A cyanate ester resin, bisphenol F-type cyanate, for example Nate ester resin and bisphenol S-type cyanate ester resin are mentioned. In addition, a prepolymerized part may be a triazine.

The said active ester resin is not specifically limited, Resin which has two or more active ester group in 1 molecule is preferable. In general, the active ester resin can be obtained by condensation of at least one of a carboxylic acid compound and a thiocarboxylic acid compound, and at least one of a hydroxy compound and a thiol compound. As this active ester resin, a dicyclopentadienyl diphenol ester compound, bisphenol A diacetate, diphenyl phthalate, diphenyl terephthalate, bis [4- (methoxycarbonyl) phenyl], etc. are mentioned.

Moreover, this active ester resin is suitable for lowering the dielectric constant and dielectric loss tangent and obtaining an electronic component having low dielectric properties.

Such a thermosetting component, a hardening | curing agent, etc. mix | blend with the well-known composition suitably tolerated according to the use characteristic of the thermosetting resin composition which uses these as a structural component, for example, the required characteristic of insulating materials, such as the interlayer insulation material of an electronic component. desirable.

In the present invention, as the thermosetting resin composition containing the thermosetting component, in addition to the above components, polymer resins such as thermoplastic resins, elastomers, rubbery particles, imidazole compounds, amine compounds, hydrazine compounds, phosphorus compounds, S-triazines Diluents, such as hardening accelerators, flame retardants, a coloring agent, and an organic solvent, such as derivatives, may also be included.

Subsequently, as a photocurable component, what is necessary is just resin which hardens by light irradiation and shows electrical insulation, For example, alkyl (meth) acrylates, such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate, for example. ; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; Mono or di (meth) acrylates of alkylene oxide derivatives such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, trishydroxyethyl isocyanurate or polyhydric (meth) acrylates of ethylene oxide or propylene oxide adducts thereof ; (Meth) acrylates of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and polyethoxydi (meth) acrylate of bisphenol A; (Meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; And melamine (meth) acrylate etc. are mentioned.

The said photocurable component is used with the photoreaction initiator which generate | occur | produces any one of a radical, a base, and an acid as needed. As this photoreaction initiator, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphineoxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphineoxide, bis- (2,6-dimethoxybenzoyl) phenylphosphineoxide, bis -(2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphineoxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphineoxide, bis- (2, Bisacylphosphine oxides such as 4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF Japan Co., Ltd., IRGACURE 819); 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, p Monoacyl phosphine oxides such as isopropyl phenylphosphinic acid isopropyl ester and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF Japan Co., Ltd., DAROCUR TPO); 1-hydroxycyclohexylphenylketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1 -{4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, 2-hydroxy-2-methyl-1-phenylpropane- Hydroxyacetophenones such as 1-one; Benzoin such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; Benzoin alkyl ethers; Benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl- 1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, N, Acetophenones such as N-dimethylaminoacetophenone; Thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 2,4-di Thioxanthones, such as isopropyl thioxanthone; Anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate and p-dimethylbenzoic acid ethyl ester; 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- Oxime esters such as 3-yl]-, 1- (0-acetyloxime); Bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (cyclopentadienyl)- Titanocenes such as bis [2,6-difluoro-3- (2- (1-phyl-1-yl) ethyl) phenyl] titanium; Phenyl disulfide 2-nitrofluorene, butyroline, anisoin ethyl ether, azobisisobutyronitrile, tetramethyl thiuram disulfide, etc. are mentioned. All of the above photoreaction initiators may be used individually by 1 type, or may be used in combination of 2 or more type.

Such a photocuring component, a photoreaction initiator, etc. are well-known compositions which are commonly used according to the use characteristic of the photocurable resin composition which consists of these as a component, for example, the required characteristic of insulating materials, such as an interlayer insulation material of an electronic component. It is preferable to mix.

In the present invention, as the photocurable resin composition containing the photocurable component, in addition to the above components, polymer resins such as thermoplastic resins, elastomers, rubber particles, diluents such as sensitizers, flame retardants, colorants, organic solvents, and other additives It may include.

In addition, when using curable resin composition of this invention as an alkali image development type photo solder resist composition which can be developed by aqueous alkali solution, it is preferable to use carboxyl group-containing resin further in addition to the above-mentioned thermosetting component and photocuring component. .

(Carboxyl group-containing resin)

As carboxyl group-containing resin, both photosensitive carboxyl group-containing resin which has one or more photosensitive unsaturated double bond, and carboxyl group-containing resin which does not have photosensitive unsaturated double bond can be used, It is not limited to a specific thing. Especially as carboxyl group-containing resin, resin enumerated below can be used suitably.

(1) Carboxyl group-containing resin obtained by copolymerization of the compound which has unsaturated carboxylic acid and an unsaturated double bond, and carboxyl group-containing resin which modified this and adjusted molecular weight and acid value.

(2) Photosensitive carboxyl group-containing resin obtained by making carboxyl group-containing (meth) acrylic-type copolymer resin react with the compound which has an oxirane ring and ethylenically unsaturated group in 1 molecule.

(3) Unsaturated monocarboxylic acid is reacted with a copolymer of a compound having one epoxy group and an unsaturated double bond and a compound having an unsaturated double bond in one molecule, and saturated or saturated with a secondary hydroxyl group produced by this reaction. Photosensitive carboxyl group-containing resin obtained by making unsaturated polybasic acid anhydride react.

(4) The photosensitive hydroxyl group and carboxyl group obtained by making a hydroxyl-containing polymer react with saturated or unsaturated polybasic acid anhydride, and then reacting the carboxylic acid produced by this reaction with the compound which has one epoxy group and unsaturated double bond in 1 molecule, respectively. Containing resin.

(5) Photosensitive carboxyl group-containing resin obtained by making a polyfunctional epoxy compound react with unsaturated monocarboxylic acid, and making polybasic acid anhydride react with one part or all part of the secondary hydroxyl group produced by this reaction.

(6) A polybasic acid anhydride is reacted with a polyfunctional epoxy compound, a compound having one reactor other than a hydroxyl group reacting with two or more hydroxyl groups and an epoxy group in one molecule, and an unsaturated group-containing monocarboxylic acid. Carboxyl group containing photosensitive resin obtained by making it react.

(7) The carboxyl group-containing photosensitive resin obtained by making unsaturated group containing monocarboxylic acid react with the reaction product of resin which has phenolic hydroxyl group, alkylene oxide, or cyclic carbonate, and making polybasic acid anhydride react with the obtained reaction product.

(8) The polyfunctional anhydride of the polybasic acid anhydride with respect to the alcoholic hydroxyl group of the reaction product obtained by making the compound which has a polyfunctional epoxy compound, the compound which has at least 1 alcoholic hydroxyl group and 1 phenolic hydroxyl group in 1 molecule, and unsaturated group containing monocarboxylic acid react Carboxyl group containing photosensitive resin obtained by making anhydride group react.

It is preferable to mix | blend this carboxyl group-containing resin with the well-known composition commonly used by alkali developing type curable resin compositions, such as the soldering resist composition which makes this resin a structural component.

It is possible to mix | blend the other conventional compounding components suitably further with curable resin composition of this invention as demonstrated above further according to the use. As other conventional compounding components, for example, as described above, polymer resins such as thermoplastic resins, elastomers, rubber particles, curing accelerators, sensitizers, flame retardants, colorants, diluents such as organic solvents, and other additives, specifically, Known conventional additives, such as an antifoamer, a leveling agent, a thixotropic agent, a thickener, a coupling agent, and a dispersing agent, etc. are mentioned.

In particular, as the colorant, conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. However, it is preferable not to contain a halogen from a viewpoint of environmental load reduction and an influence on a human body.

Red colorant:

Examples of the red colorant include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone and quinacridone.

Blue colorant, green colorant:

As the blue colorant or the green colorant, there are phthalocyanine-based and anthraquinone-based compounds, and the pigment-based compound is classified as Pigment, specifically, the color index (CI; The Society of Diaries & Colors (The Society) of Dyers and Colourists). In addition, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:

Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone and the like.

In addition, you may add coloring agents, such as purple, orange, brown, and black, for the purpose of adjusting a color tone.

The specific compounding ratio of a coloring agent can be suitably adjusted according to the kind of coloring agent to be used, the kind of other additives, etc.

As an organic solvent, Ketones, such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; Methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, etc. Glycol ethers; Esters such as ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate, and esterified products of the glycol ethers; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha and the like.

The curable resin composition of this invention containing the component as demonstrated above may be used by carrying out dry film, and may be used as it is as a liquid. In addition, when using as a liquid form, 1-component type or 2-component type or more may be sufficient.

Moreover, curable resin composition of this invention can also be used as what is called a prepreg which coated and impregnated and semi-hardened the sheet-like fibrous base materials, such as nonwoven fabric of glass cloth, glass, and aramid.

The dry film of this invention has a resin layer obtained by apply | coating and drying curable resin composition of this invention on a film (support film).

Here, when forming a dry film, first, the curable resin composition of this invention is diluted with the said organic solvent and adjusted to an appropriate viscosity, and then a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, and a transfer A roll coater, gravure coater, spray coater or the like is applied on the film in a uniform thickness. Then, a resin layer can be formed by drying the apply | coated composition at the temperature of 40-130 degreeC for 1 to 30 minutes normally. Although there is no restriction | limiting in particular about coating film thickness, Generally, it is selected suitably in the range of 3-150 micrometers, Preferably it is 5-60 micrometers in the film thickness after drying.

A resin film is used as said film (support film), For example, polyester films, such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, etc. can be used. Although there is no restriction | limiting in particular about the thickness of this film, Usually, it selects suitably in the range of 10-150 micrometers. More preferably, it is the range of 15-130 micrometers.

Thus, with respect to the film in which the resin layer containing curable resin composition of this invention was formed, the film (protective film) which can be peeled off to the surface of a resin layer for the purpose of preventing sticking to the surface of a resin layer, etc. It is preferable to further laminate.

As this peelable film, when peeling, the adhesive force with a resin layer should be smaller than the adhesive force between a resin layer and a support film, For example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, the surface-treated paper, etc. Can be used.

The cured product of the present invention is obtained by curing the curable resin composition of the present invention or the resin layer in the dry film of the present invention. Such hardened | cured material of this invention can be used suitably as electronic component materials, such as a soldering resist, an interlayer insulation material, and a hole filling material which require insulation reliability.

The electronic component of this invention is equipped with the hardened | cured material of the said invention, Specifically, a printed wiring board etc. are mentioned. In particular, by setting it as a multilayer printed wiring board using the curable resin composition of the said invention as an interlayer insulation material, it can be set as having favorable interlayer insulation reliability.

<Other blended components except fillers other than the fine powder and the fine powder according to the second to fifth objects>

In the 1st aspect of this invention, as another compounding component except the fine powder which concerns on 2nd-5th objective, and filler other than fine powder, it is as follows.

Regarding the second object of the present invention, the curable resin composition of the present invention preferably contains a cyclic ether compound having at least any one of a naphthalene skeleton and an anthracene skeleton as the curable resin.

Thus, by using the cyclic ether compound which has at least any one of a naphthalene skeleton and an anthracene skeleton, when it is set as the electronic component of a laminated structure, interlayer migration can be suppressed and a favorable interlayer insulation reliability can be obtained by this. Can be. In particular, since migration easily occurs on the surface of the insulating layer roughened by the desmear process, the present invention is useful in that it is easy to ensure insulation reliability between layers even in such a case.

In addition, the effect of lowering the thermal expansion property by blending the fine powder is remarkably expressed in hydrophilicity among the fine powder. Since such fine powder has a large quantum effect on optical, electrical, and magnetic properties, physical properties such as reactivity and electrical properties may change, and unexpected changes may occur. When the electronic component of the laminated structure like this time is used, it is thought that this is because of the low insulation reliability between layers. In the case where the fine powder is hydrophilic particles such as, for example, fine cellulose fibers, migration between layers is particularly poor. This can be solved by using a cyclic ether compound having at least one of a naphthalene skeleton and an anthracene skeleton.

[Cyclic ether compound having at least one kind of naphthalene skeleton and anthracene skeleton]

The cyclic ether compound having a naphthalene skeleton is a compound having a structure derived from a naphthalene skeleton or a naphthalene skeleton and having a cyclic ether. Although the cyclic ether compound which has a naphthalene skeleton is not specifically limited, It is preferable to have 2 or more cyclic ether in 1 molecule. The cyclic ether may be a cyclic thioether.

As a commercial item, epiclon HP-4032, HP-4032D, HP-4700, HP-4770, HP-5000 (all made in DIC Corporation), NC-7000L, NC-7300L, NC-7700L (all Nippon Kayaku (all Co., Ltd.), ZX-1355, ESN-155, ESN-185V, ESN-175, ESN-355, ESN-375, ESN-475V, ESN-485 (all from Shinnitetsu Sumikin Kagaku Co., Ltd.) Can be mentioned.

The cyclic ether compound having an anthracene skeleton is a compound having a structure derived from an anthracene skeleton or an anthracene skeleton and having a cyclic ether. Although the cyclic ether compound which has an anthracene skeleton is not specifically limited, It is preferable to have 2 or more cyclic ether in 1 molecule. The cyclic ether may be a cyclic thioether.

As a commercial item, YX-8800 (made by Mitsubishi Chemical Corporation) etc. is mentioned.

The compounding quantity of the cyclic ether compound which has at least any 1 type of a naphthalene frame | skeleton and an anthracene frame | skeleton becomes like this. Preferably it is 0.5 mass% or more and 80 mass% or less with respect to the total amount of the composition except a solvent, More preferably, it is 1 mass% or more and 40 mass% % Or less, More preferably, they are 1.5 mass% or more and 30 mass% or less. When the compounding quantity of the said cyclic ether compound is 0.5 mass% or more, the fall of insulation reliability between layers resulting from a fine cellulose fiber can be prevented. On the other hand, when it is 80 mass% or less, sclerosis | hardenability improves.

In the present invention, the cyclic ether compound having at least one of the naphthalene skeleton and the anthracene skeleton has a function as a curable resin, and a cyclic ether compound having a naphthalene skeleton and a cyclic ether compound having an anthracene skeleton, respectively, alone. You may use it or use it together.

In this invention, curable resin, such as thermosetting resin and photocurable resin other than the cyclic ether compound which has at least any one of a naphthalene skeleton and an anthracene skeleton, can be used together according to the objective.

According to the third object of the present invention, the curable resin composition of the present invention is at least one member selected from the group consisting of a cyclic resin compound having a dicyclopentadiene skeleton and a phenol resin having a dicyclopentadiene skeleton as the curable resin. It is preferable to include.

As described above, by using at least one selected from the group consisting of a cyclic ether compound having a dicyclopentadiene skeleton and a phenol resin having a dicyclopentadiene skeleton, the relative dielectric constant and dielectric loss tangent are reduced to have low dielectric properties. Electronic components can be obtained. On the other hand, by using fine powder, the adhesiveness of hardened | cured material and plating copper can be ensured and a highly accurate circuit formation can be made possible.

Moreover, the fine powder used for this invention mix | blends with curable resin which has a dicyclopentadiene frame | skeleton with low adhesiveness with plating copper, and the hardened | cured material of the composition containing such curable resin is adhesiveness with very high plating copper. Is obtained. In addition, this effect is obtained without reducing the dielectric properties derived from the dicyclopentadiene skeleton.

[A cyclic ether compound having a dicyclopentadiene skeleton and a phenol resin having a dicyclopentadiene skeleton]

The cyclic ether compound having a dicyclopentadiene skeleton has a structure derived from a dicyclopentadiene skeleton or a dicyclopentadiene skeleton and is a compound having a cyclic ether. The cyclic ether compound having a dicyclopentadiene skeleton is not particularly limited, but one having two or more cyclic ethers in one molecule is preferable. The cyclic ether may be a cyclic thioether.

As a commercial item, Epiclonal HP-7200, HP-7200H, HP-7200L (all made by DIC Corporation), XD-1000-1L, XD-1000-2L (all made by Nippon Kayaku Co., Ltd.), Tactix 558, Tactix 756 (all manufactured by Huntsman Advanced Materials).

The phenol resin which has a dicyclopentadiene frame | skeleton is a compound which has a structure derived from a dicyclopentadiene frame | skeleton or a dicyclopentadiene frame | skeleton, and has a phenolic hydroxyl group. The phenol resin having a dicyclopentadiene skeleton is not particularly limited, but one having two or more phenolic hydroxyl groups in one molecule is preferable. As a commercial item, cash register GDP-6085, cash register GDP-6095LR, cash register GDP-6095HR, cash register GDP-6115L, cash register GDP-6115H, cash register GDP-6140 (all made by Gunei Kagaku Kogyo Kogyo), J- DPP-95, J-DPP-115 (all are JFE Chemical Co., Ltd.), etc. are mentioned.

The amount of at least one compound selected from the group consisting of a cyclic ether compound having a dicyclopentadiene skeleton and a phenol resin having a dicyclopentadiene skeleton is preferably 0.5% by mass or more and 80 to the total amount of the composition excluding the solvent. Mass% or less, More preferably, they are 1 mass% or more and 40 mass% or less, More preferably, they are 1.5 mass% or more and 30 mass% or less. When the compounding quantity of at least 1 sort (s) chosen from the group which consists of a cyclic ether compound which has a dicyclopentadiene frame | skeleton, and a phenol resin which has a dicyclopentadiene skeleton is 0.5 mass% or more, low dielectric properties can be obtained favorably. On the other hand, when it is 80 mass% or less, sclerosis | hardenability improves.

In the present invention, at least one selected from the group consisting of a cyclic ether compound having the dicyclopentadiene skeleton and a phenol resin having a dicyclopentadiene skeleton has a function as a curable resin and has a dicyclopentadiene skeleton. The cyclic ether compound to have and the phenol resin which has a dicyclopentadiene skeleton may be used independently, or may be used together.

In the present invention, a thermosetting resin or photocurable resin other than at least one selected from the group consisting of a cyclic ether compound having a dicyclopentadiene skeleton and a phenol resin having a dicyclopentadiene skeleton is furthermore, according to the purpose. Of curable resin can be used together.

Regarding the fourth object of the present invention, the curable resin composition of the present invention preferably contains a phenoxy resin as the curable resin.

Thus, by using a phenoxy resin and fine powder, it is possible to remove a smear in a short time in a desmear process, and since the surface roughness of hardened | cured material can be suppressed small, it is possible to transmit a high frequency efficiently. do. On the other hand, even if surface roughness is small, the adhesiveness of hardened | cured material and plated copper can also be ensured, and high precision circuit formation is attained.

Moreover, by using the fine powder which concerns on this invention, the hardened | cured material of the composition containing such a fine powder can remove a smear easily, and also adhesiveness with plating copper, suppressing the surface roughness of hardened | cured material small You can also secure. This effect is expressed by the combination with the phenoxy resin mentioned later. In addition, this effect is remarkably expressed in hydrophilicity among fine powder.

[Phenoxy Resin]

Phenoxy resins are generally synthesized from bisphenols and epichlorohydrin. The bisphenols used are bisphenol A type, bisphenol F type, bisphenol S type, biphenyl type, bisphenol acetophenone type, fluorene type, trimethylcyclohexane type, terpene type, and the like. have. The phenoxy resin is not particularly limited, but the terminal epoxy type is preferable when the photocurable composition is used. As a commercial item, 1256, 4250, 4275, YX8100, YX6954, YL7213, YL7290, YL7482 (all made by Mitsubishi Kagaku Co., Ltd.), FX280, FX293, YP50, YP50S, YP55, YP70, YPB-43C (all Shinnitetsu Sumikin) Kagaku Co., Ltd., PKHB, PKHC, PKHH, PKHJ, PKFE, PKHP-200, PKCP-80 (all are the InChem company make), etc. are mentioned.

The blending amount of the phenoxy resin is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.3% by mass or more and 30% by mass or less, and still more preferably 0.5% by mass or more 10 based on the total amount of the composition excluding the solvent. It is mass% or less. When the compounding quantity of phenoxy resin is 0.1 mass% or more, the removal of smear resulting from fine powder, and the adhesiveness of a conductor improve. On the other hand, when it is 50 mass parts or less, sclerosis | hardenability improves.

In this invention, curable resin, such as thermosetting resin other than a phenoxy resin, photocurable resin, can be used together further according to the objective.

Regarding the fifth object of the present invention, the curable resin composition of the present invention includes, as the curable resin, at least one selected from the group consisting of a cyclic ether compound having a biphenyl skeleton and a phenol resin having a biphenyl skeleton. desirable.

Thus, when mounting plating copper in solid form on hardened | cured material by using at least 1 sort (s) chosen from the group which consists of a cyclic ether compound which has a biphenyl skeleton, and a phenol resin which has a biphenyl skeleton, component mounting etc. The expansion of the plated copper can be suppressed by the thermal history of.

In addition, the effect of lowering the thermal expansion property by blending the fine powder is remarkably expressed in hydrophilicity among the fine powder. On the other hand, when the fine powder is hydrophilic particles such as, for example, fine cellulose fibers, it is considered that expansion at high temperature in the solid-plated copper is particularly likely to occur, so that the application of the present invention is useful. .

[At least 1 kind selected from the group which consists of a cyclic ether compound which has a biphenyl skeleton, and a phenol resin which has a biphenyl skeleton]

The cyclic ether compound having a biphenyl skeleton has a structure derived from a biphenyl skeleton or a biphenyl skeleton, and is a compound having a cyclic ether. Although the cyclic ether compound which has a biphenyl skeleton is not specifically limited, It is preferable to have 2 or more cyclic ether in 1 molecule. The cyclic ether may be a cyclic thioether.

As a commercial item, NC-3000H, NC-3000L, NC-3100 (all made by Nippon Kayaku Co., Ltd.), YX-4000, YX4000H, YL-6121 (all made by Mitsubishi Kagaku Co., Ltd.), Denacol EX-412 (Nagase Chemtex Co., Ltd. product) etc. are mentioned.

The compounding quantity of the cyclic ether compound which has a biphenyl skeleton becomes like this. Preferably it is 0.5 mass% or more and 80 mass% or less with respect to the total amount of the composition except a solvent, More preferably, it is 1 mass% or more and 40 mass% or less, More preferably, It is 1.5 mass% or more and 30 mass% or less. When the compounding quantity of the said compound is 0.5 mass% or more, expansion of the plating copper resulting from fine particle can be prevented. On the other hand, when it is 80 mass% or less, sclerosis | hardenability improves.

The phenol resin which has a biphenyl skeleton is a compound which has a structure derived from a biphenyl skeleton or a biphenyl skeleton, and has a phenolic hydroxyl group. Although the phenol resin which has a biphenyl skeleton is not specifically limited, It is preferable to have two or more phenolic hydroxyl groups in 1 molecule. As a commercial item, GPH-65, GPH-103 (made by Nippon Kayaku Co., Ltd.), MEH-7851SS, MEH-7851M, MEH-7851-4H, MEH-7851-3H (made by Meiwa Kasei Co., Ltd.), HE200 (Air Water Co., Ltd. product) etc. are mentioned.

The compounding quantity of the phenol resin which has a biphenyl skeleton becomes like this. Preferably it is 0.5 mass% or more and 60 mass% or less with respect to the total amount of the composition except a solvent, More preferably, it is 1 mass% or more and 30 mass% or less, More preferably, 1.5 It is mass% or more and 20 mass% or less. When the compounding quantity of the said compound is 0.5 mass% or more, expansion of the plating copper resulting from fine particle can be prevented. On the other hand, when it is 60 mass% or less, sclerosis | hardenability improves.

In the present invention, at least one selected from the group consisting of the cyclic ether compound having a biphenyl skeleton and the phenol resin having a biphenyl skeleton has a function as a curable resin, and has a cyclic ether compound having a biphenyl skeleton; The phenol resin which has a biphenyl skeleton may be used independently, or may be used together.

In the present invention, curable resins such as thermosetting resins and photocurable resins other than at least one selected from the group consisting of a cyclic ether compound having a biphenyl skeleton and a phenol resin having a biphenyl skeleton, may be further used according to the purpose. It can be used together.

(Thermosetting resin)

As a thermosetting resin, what is necessary is just resin which hardens by heating and shows electrical insulation, For example, bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol E-type epoxy resin, bisphenol M-type epoxy resin, Bisphenol-type epoxy resins, such as bisphenol P-type epoxy resin and bisphenol Z-type epoxy resin, bisphenol-A novolak-type epoxy resin, phenol novolak-type epoxy resin, novolak-type epoxy resins, such as cresol novolak epoxy resin, and biphenyl type epoxy Resin, biphenyl aralkyl type epoxy resin, arylalkylene type epoxy resin, tetraphenylolethane type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, flu Orene type epoxy resin, glycidyl methacrylate copolymer type epoxy resin, cyclohexyl male Copolymerized epoxy resin of imide and glycidyl methacrylate, epoxy modified polybutadiene rubber derivative, CTBN modified epoxy resin, trimethylolpropanepolyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl -4,4'- diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris (2,3-epoxy Propyl) isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, phenol novolak resin, cresol novolak resin, bisphenol A novolak resin and other novolak type phenolic resins, unmodified resol Triazine ring-containing resins, such as phenol resins such as phenolic resins, phenoxy resins, urea (urea) resins, melamine resins, and unsaturated resins such as phenolic resins, oil-modified resolphenol resins modified with linseed oil, walnut oil, On poly Tere resin, bismaleimide resin, diallyl phthalate resin, silicone resin, resin having a benzoxazine ring, norbornene-based resin, cyanate resin, isocyanate resin, urethane resin, benzocyclobutene resin, maleimide resin, bismaleimide Triazine resin, polyazomethine resin, thermosetting polyimide, dicyclopentadienyl diphenol ester compound, bisphenol A diacetate, diphenyl phthalate, diphenyl terephthalate, bis [tetraphthalic acid bis [4- (methoxycarbonyl) phenyl] Active ester compounds and the like. Especially, when an active ester compound is used, since thermal expansion in a high temperature range can be reduced and low thermal expansion rate can be ensured favorably, it is preferable.

(Photocurable resin (radical polymerization))

As such photocurable resin, what is necessary is just resin which hardens | cures by active energy ray irradiation and shows electrical insulation, In particular, the compound which has one or more ethylenically unsaturated bond in a molecule | numerator is used preferably. As the compound having an ethylenically unsaturated bond, known conventional photopolymerizable oligomers, photopolymerizable vinyl monomers, and the like are used.

Examples of the photopolymerizable oligomer include unsaturated polyester oligomers, (meth) acrylate oligomers, and the like. As a (meth) acrylate type oligomer, epoxy (meth) acrylates, such as phenol novolak epoxy (meth) acrylate, cresol novolak epoxy (meth) acrylate, and bisphenol-type epoxy (meth) acrylate, urethane (meth) Acrylate, epoxyurethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene modified (meth) acrylate, and the like. In addition, in this specification, a (meth) acrylate is a term used generically for acrylate, methacrylate, and mixtures thereof, and the same also about other similar expression.

As a photopolymerizable vinyl monomer, well-known conventional things, for example, styrene derivatives, such as styrene, chloro styrene, (alpha) -methylstyrene; Vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; Vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinylcyclohexyl ether, ethylene glycol monobutyl vinyl Vinyl ethers such as ether and triethylene glycol monomethyl vinyl ether; Such as acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, and N-butoxymethylacrylamide Meta) acrylamides; Allyl compounds such as triallyl isocyanurate, diallyl phthalate and diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isoboroyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth Esters of (meth) acrylic acid such as acrylate; Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and pentaerythritol tri (meth) acrylate; Alkoxyalkylene glycol mono (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; Ethylene glycol di (meth) acrylate, butanediol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate Alkylene polyol poly (meth) acrylates such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Polyoxyalkylene glycol polys such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxylated trimethylolpropane triacrylate and propoxylated trimethylolpropane tri (meth) acrylate ( Meta) acrylates; Poly (meth) acrylates such as hydroxypivalate neopentyl glycol ester di (meth) acrylate; Isocyanurate type poly (meth) acrylates, such as a tris [(meth) acryloxyethyl] isocyanurate, etc. are mentioned.

(Photocurable resin (cationic polymerization))

As such a photocurable resin, an alicyclic epoxy compound, an oxetane compound, a vinyl ether compound, etc. can be used suitably. Among these, examples of the alicyclic epoxy compound include 3,4,3 ', 4'-diepoxybicyclohexyl, 2,2-bis (3,4-epoxycyclohexyl) propane, and 2,2-bis (3,4-epoxy Cyclohexyl) -1,3-hexafluoropropane, bis (3,4-epoxycyclohexyl) methane, 1- [1,1-bis (3,4-epoxycyclohexyl)] ethylbenzene, bis (3, 4-epoxycyclohexyl) adipate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, (3,4-epoxy-6-methylcyclohexyl) methyl-3 ', 4' -Epoxy-6-methylcyclohexanecarboxylate, ethylene-1,2-bis (3,4-epoxycyclohexanecarboxylic acid) ester, cyclohexene oxide, 3,4-epoxycyclohexylmethyl alcohol, 3,4 Alicyclic epoxy compounds etc. which have epoxy groups, such as-epoxycyclohexyl ethyl trimethoxysilane, are mentioned. As a commercial item, For example, Celoxide 2000, Celoxide 2021, Celoxide 3000, EHPE3150 by Daicel Kagaku Kogyo Co., Ltd .; Epomic VG-3101 by Mitsui Chemicals, Inc .; E-1031S by Yuka Shell Epoxy Co., Ltd .; TETRAD-X and TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Ltd .; Nippon Soda Co., Ltd. EPB-13, EPB-27, etc. are mentioned.

Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether and 1,4-bis [(3- Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methylacrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers thereof Or in addition to polyfunctional oxetanes such as copolymers, oxetane alcohols and novolac resins, poly (p-hydroxystyrenes), cardo-type bisphenols, calix arenes, calyx resorcinrenes or silsesquioxanes And oxetane compounds such as ether copolymers with resins having hydroxyl groups, such as copolymers of unsaturated monomers having an oxetane ring and alkyl (meth) acrylates. As a commercial item, Eternacol OXBP, OXMA, OXBP, EHO, xylylenebisoxetane, Alonoxetane OXT-101, OXT-201, OXT- made by Ube Kosan Co., Ltd. is made, for example. 211, OXT-221, OXT-212, OXT-610, PNOX-1009, etc. are mentioned.

As a vinyl ether compound, Cyclic ether type vinyl ether (vinyl ether which has cyclic ether groups, such as an oxirane ring, an oxetane ring, an oxolane ring), such as iso sorbitol divinyl ether and oxanorbornene divinyl ether; Aryl vinyl ethers such as phenyl vinyl ether; alkyl vinyl ethers such as n-butyl vinyl ether and octyl vinyl ether; Cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; Polyfunctional vinyl ethers such as hydroquinonedivinylether, 1,4-butanedioldivinylether, cyclohexanedivinylether, cyclohexanedimethanoldivinylether, and substituents such as alkyl groups and allyl groups at the α and / or β positions Vinyl ether compound which has, etc. are mentioned. As a commercial item, for example, 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 2-hydroxybutyl vinyl ether (HBVE) made by Maruzen Sekiyu Chemical Co., Ltd., tri Ethylene glycol divinyl ether, etc. are mentioned.

Moreover, when using curable resin composition of this invention as an alkali image development type photo solder resist which can be developed by aqueous alkali solution, it is also preferable to use carboxyl group-containing resin.

(Carboxyl group-containing resin)

As carboxyl group-containing resin, both photosensitive carboxyl group-containing resin which has one or more photosensitive unsaturated double bond, and carboxyl group-containing resin which does not have photosensitive unsaturated double bond can be used, It is not limited to a specific thing. Especially as carboxyl group-containing resin, resin enumerated below can be used suitably.

(1) Carboxyl group-containing resin obtained by copolymerization of the compound which has unsaturated carboxylic acid and an unsaturated double bond, and carboxyl group-containing resin which modified this and adjusted molecular weight and acid value.

(2) Photosensitive carboxyl group-containing resin obtained by making carboxyl group-containing (meth) acrylic-type copolymer resin react with the compound which has an oxirane ring and ethylenically unsaturated group in 1 molecule.

(3) Unsaturated monocarboxylic acid is reacted with a copolymer of a compound having one epoxy group and an unsaturated double bond and a compound having an unsaturated double bond in one molecule, and saturated or saturated with a secondary hydroxyl group produced by this reaction. Photosensitive carboxyl group-containing resin obtained by making unsaturated polybasic acid anhydride react.

(4) The photosensitive hydroxyl group and carboxyl group obtained by making a hydroxyl-containing polymer react with saturated or unsaturated polybasic acid anhydride, and then reacting the carboxylic acid produced by this reaction with the compound which has one epoxy group and unsaturated double bond in 1 molecule, respectively. Containing resin.

(5) Photosensitive carboxyl group-containing resin obtained by making a polyfunctional epoxy compound react with unsaturated monocarboxylic acid, and making polybasic acid anhydride react with one part or all part of the secondary hydroxyl group produced by this reaction.

(6) A polybasic acid anhydride is reacted with a polyfunctional epoxy compound, a compound having one reactor other than a hydroxyl group reacting with two or more hydroxyl groups and an epoxy group in one molecule, and an unsaturated group-containing monocarboxylic acid. Carboxyl group containing photosensitive resin obtained by making it react.

(7) The carboxyl group-containing photosensitive resin obtained by making unsaturated group containing monocarboxylic acid react with the reaction product of resin which has phenolic hydroxyl group, alkylene oxide, or cyclic carbonate, and making polybasic acid anhydride react with the obtained reaction product.

(8) The polyfunctional anhydride of the polybasic acid anhydride with respect to the alcoholic hydroxyl group of the reaction product obtained by making the compound which has a polyfunctional epoxy compound, the compound which has at least 1 alcoholic hydroxyl group and 1 phenolic hydroxyl group in 1 molecule, and unsaturated group containing monocarboxylic acid react Carboxyl group containing photosensitive resin obtained by making anhydride group react.

[filler]

It is preferable to further contain fillers other than fine powder in curable resin composition of this invention. Examples of the filler include barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, and the like. Among these fillers, silica and spherical silica are preferred among them because of their low specific gravity, being able to be blended in a composition at a high ratio, and excellent in low thermal expansion. It is preferable that it is 3 micrometers or less, and, as for the average particle diameter of a filler, 1 micrometer or less is more preferable. In addition, the average particle diameter of a filler can be calculated | required by the laser diffraction type particle diameter distribution measuring apparatus.

The compounding quantity of a filler is 1-90 mass% in the total amount of the composition except a solvent, Preferably it is 2-80 mass%, More preferably, it is 5-75 mass%. By carrying out the compounding quantity of a filler in the said range, the coating film performance of the hardened | cured material after hardening can be ensured favorably.

In addition to curable resin composition of this invention, it is possible to mix | blend other conventional compounding components suitably according to the use. As another conventional compounding component, a curing catalyst, a photoinitiator, a coloring agent, an organic solvent, etc. are mentioned, for example.

As a curing catalyst, it is a phenol compound; Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2- Imidazole derivatives such as phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine Hydrazine compounds such as compounds, adipic dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc. are mentioned. Moreover, as a commercial item, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (made by Shikoku Kasei Kogyo Co., Ltd.), U-CAT3503N, U-CAT3502T, DBU, DBN, U-CATSA102, U-CAT5002 (Made by San Apro Co., Ltd.) etc. are mentioned, You may use individually or in mixture of 2 or more types. Similarly, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S- Triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanur S-triazine derivatives, such as an acid adduct, can also be used.

In this invention, a phenolic compound is used preferably especially. As a phenolic compound, for example, a phenol novolak resin, an alkylphenol novolak resin, a triazine structure containing novolak resin, bisphenol A novolak resin, a dicyclopentadiene type phenol resin, a xyloxic phenol resin, a copna resin, a terpene Known and conventional ones such as phenol compounds such as modified phenol resins and polyvinyl phenols, naphthalene curing agents and fluorene curing agents can be used alone or in combination of two or more thereof. As said phenolic compound, HE-610C, 620C by Air Water Corporation, TD-2131, TD-2106, TD-2093, TD-2091, TD-2090, VH-4150, VH by DIC Corporation -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, SN-170, SN180, SN190, SN475, SN485, SN495, SN375, SN395, JX made by Shinnitetsu Sumikin Kagaku Co., Ltd. DPP, Meiwa Kasei Co., Ltd. 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, Mitsui Chemicals Co., Ltd. XL, XLC, RN, RS, RX etc. are mentioned, However, It is not limited to these. These phenolic compounds can be used individually or in combination of 2 or more types.

The compounding quantity of the curing catalyst used for this invention is sufficient in the ratio normally used, and, for example, in the case of a phenol compound, it is 1-150 mass parts, Preferably it is 5-100 mass parts, with respect to 100 mass parts of thermosetting resins, More preferably, it is 10-50 mass parts, and in the case of other curing catalysts, it is 0.01-10 mass parts, Preferably it is 0.05-5 mass parts, More preferably, it is 0.1-3 mass parts.

The photoinitiator is for curing the photocurable resin among the curable resins, and may be a radical photopolymerization initiator or a photocationic polymerization initiator.

As an optical radical polymerization initiator, For example, benzoin and benzoin alkyl ether, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone- Aminoalkyl phenones such as 1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone; Thioxanthones, such as 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, and 2, 4- diisopropyl thioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone; Or xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphineoxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine Phosphine oxides such as oxides and ethyl-2,4,6-trimethylbenzoylphenylphosphinate; Various peroxides, titanocene type initiator, etc. are mentioned. These may be used in combination with photosensitizers such as tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine. You may also

As a photocationic polymerization initiator, For example, Onium salts, such as a diazonium salt, an iodonium salt, a bromonium salt, a chloronium salt, a sulfonium salt, a selenium salt, a pyryllium salt, a thiapyryllium salt, a pyridinium salt; Halogenated compounds such as tris (trihalomethyl) -s-triazine and derivatives thereof; 2-nitrobenzyl ester of sulfonic acid; Iminosulfonate; 1-oxo-2-diazonaphthoquinone-4-sulfonate derivatives; N-hydroxyimide = sulfonate; Tri (methanesulfonyloxy) benzene derivative; Bissulfonyl diazomethanes; Sulfonylcarbonylalkanes; Sulfonylcarbonyldiazomethanes; Disulfone compound etc. are mentioned.

These photoinitiators can be used individually or in combination of 2 or more types.

The compounding quantity of a photoinitiator is 0.05-10 mass parts, Preferably it is 0.1-8 mass parts, More preferably, it is 0.3-6 mass parts with respect to 100 mass parts of photocurable resins in solid content conversion. By mix | blending a photoinitiator in this range, the photocurability on copper becomes sufficient, the curability of a coating film becomes favorable, coating film characteristics, such as chemical resistance, improves, and deep-curing property also improves.

As a coloring agent, conventionally well-known coloring agents, such as red, blue, green, and yellow, can be used, and any of a pigment, dye, and a pigment may be sufficient. However, it is preferable not to contain a halogen from a viewpoint of environmental load reduction and an influence on a human body.

Blue colorant:

As the blue colorant, there are phthalocyanine-based and anthraquinone-based pigments, and the pigment-based compound is classified as Pigment, specifically, the following color index (CI; The Society of Diamonds & Colors (The Society of Dyers and Colourists) are numbered: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pig Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60.

As dye system, 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 may be used. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:

Examples of the green colorant include phthalocyanine series and anthraquinone series, and specifically, pigment green 7, pigment green 36, solvent green 3, solvent green 5, solvent green 20, solvent green 28, and the like can be used. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:

Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like. Specific examples include the following.

Anthraquinones: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

Isoindolinone series: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

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 series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.

Monoazo series: 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.

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

Red colorant:

Examples of the red colorant include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone and quinacridone. It can be mentioned.

Monoazo series: 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.

Disazo meter: Pigment Red 37, 38, 41.

Monoazo 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 series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.

Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224 .

Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

Condensation azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.

Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.

Quinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

In addition, you may add coloring agents, such as purple, orange, brown, and black, for the purpose of adjusting a color tone.

Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment There are 23 Brown, CI Pigment Brown 25, CI Pigment Black 1, and CI Pigment Black 7.

The specific compounding ratio of a coloring agent can be suitably adjusted according to the kind of coloring agent to be used, the kind of other additives, etc.

As an organic solvent, Ketones, such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; Methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, etc. Glycol ethers; Esters such as ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate, and esterified products of the glycol ethers; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha and the like.

Moreover, if necessary, additives known in general, such as an antifoamer, a leveling agent, a thixotropic imparting agent, a thickener, a coupling agent, a dispersing agent, and a flame retardant, can be contained.

The curable resin composition of this invention may be used for dry film forming, or may be used as a liquid phase. Moreover, curable resin composition of this invention can also be used as a prepreg coated and impregnated and semi-hardened to sheet-like fibrous base materials, such as a nonwoven fabric of glass cloth, glass, and aramid. In the case of using as a liquid, it may be one-liquid or two-liquid or more. As the two-component composition, for example, at least one selected from the group consisting of fine cellulose fibers, a cyclic ether compound having a naphthalene skeleton and a cyclic ether compound having an anthracene skeleton, a cyclic ether compound having a dicyclopentadiene skeleton and a dish At least one selected from the group consisting of a phenol resin having a clopentadiene skeleton, a phenoxy resin, or at least one selected from the group consisting of a cyclic ether compound having a biphenyl skeleton and a phenol resin having a biphenyl skeleton, It is good also as a composition divided.

The dry film of this invention has a resin layer obtained by apply | coating and drying curable resin composition of this invention on a carrier film. When forming a dry film, first, the curable resin composition of this invention is diluted with the said organic solvent, adjusted to an appropriate viscosity, and then a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, and a transfer roll coater By a gravure coater, spray coater or the like, is applied on the carrier film with a uniform thickness. Then, a resin layer can be formed by drying the apply | coated composition at the temperature of 40-130 degreeC for 1 to 30 minutes normally. Although there is no restriction | limiting in particular about coating film thickness, Generally, it is selected suitably in the range of 3-150 micrometers, Preferably it is 5-60 micrometers in the film thickness after drying.

As a carrier film, a plastic film is used, For example, polyester films, such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, etc. can be used. Although there is no restriction | limiting in particular about the thickness of a carrier film, Usually, it selects suitably in the range of 10-150 micrometers. More preferably, it is the range of 15-130 micrometers.

After forming the resin layer which consists of curable resin composition of this invention on a carrier film, the cover film which can be peeled off to the surface of a resin layer is further carried out for the purpose of preventing dust from adhering to the surface of a resin layer. It is preferable to laminate. As a peelable cover film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, the surface-treated paper, etc. can be used, for example. As a cover film, when peeling a cover film, the adhesive force between a resin layer should just be smaller than the adhesive force of a resin layer and a carrier film.

Moreover, in this invention, you may form a resin layer by apply | coating and drying curable resin composition of this invention on the said cover film, and laminating | stacking a carrier film on the surface. That is, when manufacturing a dry film in this invention, you may use any of a carrier film and a cover film as a film which apply | coats curable resin composition of this invention.

The cured product of the present invention is obtained by curing the resin layer in the curable resin composition of the present invention or the dry film of the present invention.

The electronic component of this invention is equipped with the hardened | cured material of the said invention, Specifically, a printed wiring board etc. are mentioned. The hardened | cured material of this invention can be used suitably in the electronic component which requires insulation reliability between layers. In particular, by setting it as a multilayer printed wiring board using the curable resin composition of the said invention as an interlayer insulation material, it can be set as having favorable interlayer insulation reliability.

In FIG. 2-1 (FIG. 3-1, FIG. 4-1, FIG. 5-1), the partial cross section which shows one structural example of the multilayer printed wiring board which concerns on an example of the electronic component of this invention is shown. The multilayer printed wiring board shown in figure can be manufactured as follows, for example. First, a through hole is formed in the core substrate 2 in which the conductor pattern 1 was formed. Formation of a through hole can be performed by a suitable means, such as a drill, a metal mold punch, and a laser beam. Thereafter, a roughening treatment is performed using a roughening agent. Generally, the roughening treatment is swelled with an organic solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, methoxypropanol or an alkaline aqueous solution such as caustic soda, caustic kali, and the like. It is performed using an oxidizing agent such as permanganate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like.

Next, the conductor pattern 3 is formed by a combination of electroless plating and electrolytic plating. The process of forming a conductor layer by electroless plating is a process of immersing in the aqueous solution containing a catalyst for plating, adsorbing a catalyst, and then immersing in a plating liquid, and depositing plating. According to a conventional method (subtractive method, semi-additive method, etc.), a predetermined circuit pattern is formed on the surface conductor layer of the core substrate 2, and as shown, the conductor patterns 3 are formed on both sides. do. At this time, a plating layer is formed in the through hole, and as a result, the connection part 4 of the conductor pattern 3 of the multilayer printed wiring board and the connection part 1a of the conductor pattern 1 are electrically connected to each other. The hole 5 is formed.

Subsequently, the thermosetting composition is applied, for example, by a screen printing method, a spray coating method, a curtain coating method, or the like, followed by heat curing to form the interlayer insulating layer 6. When using a dry film or a prepreg, it laminates or hot-presses and heat-cures, and forms the interlayer insulation layer 6. Subsequently, vias 7 for electrically connecting the connection portions of the respective conductor layers are formed by appropriate means such as, for example, laser light, and the conductor pattern 8 is formed in the same manner as the conductor pattern 3. Form. In addition, the interlayer insulating layer 9, the vias 10, and the conductor pattern 11 are formed in the same manner. Then, a multilayer printed wiring board is manufactured by forming the soldering resist layer 12 in outermost layer. In the above, although the example which forms an interlayer insulation layer and a conductor layer on the laminated board | substrate was demonstrated, you may use a single-sided board or a double-sided board instead of a laminated board | substrate.

<< 2nd aspect of this invention >>

Curable resin composition of a 2nd aspect of this invention is characterized by including (A) at least one dimension with fine powder smaller than 100 nm, and (B) thermosetting component.

According to the characteristic structure of such a 2nd aspect of this invention, in the printed wiring board which has at least one of a recessed part and a through hole, also in the recessed part, such as via-holes and through-holes filled with the resin filler, even in the high temperature heating at the time of component mounting. The effect peculiar to the present invention can be obtained that expansion does not occur in wiring such as a conductor pad or a via hole on a hole.

Although the detailed mechanism is not clear about expansion of the wiring in this high temperature heating, it is thought that the cause is large in the difference of the thermal expansion coefficient at the high temperature of the via-hole and through-hole formed from copper, and the resin filler.

Generally, the method of mix | blending a large amount of an inorganic filler is known in order to make organic substances, such as resin, small to the thermal expansion coefficient close to a metal. According to this method, it is possible to make the thermal expansion coefficient near the metal certainly close to the metal, but in the case of high temperature heating such as component mounting, the thermal expansion coefficient is still much larger than the metal even when a large amount of filler is contained. For this reason, it is thought that a resin filler expands up and down of a through hole, for example at the time of high temperature heating. In addition, since pressure is applied to the wall surface of the through hole and the bottom of the via hole which suppress the expansion, reliability degradation such as disconnection also occurs.

In this regard, according to the present invention, since fine powders such as fine cellulose fibers are dispersed in the resin filler, reinforcing effects are expressed by taking interactions in which the fine powders are attracted to each other. The rise can be suppressed, and as a result, it is thought that the unique effect of the expansion of the wiring in high temperature heating does not occur.

Moreover, according to the characteristic structure of such a 2nd aspect of this invention, in the manufacturing method of the printed wiring board which has at least one of a recessed part and a through hole, at the time of hardening of the curable resin composition filled in the recessed part and a through hole, a filler component The effect peculiar to the present invention that there is no bleeding of this lean resin composition can be obtained.

Although the detailed mechanism is not clear about the bleeding of the resin component in which the filler component at the time of hardening is sparse, it is thought that it originates in using a liquid thing necessarily as a resin component in order to adjust a viscosity. It is preferable that a resin filler filled in recesses or through holes such as via holes, through holes, etc. is not used as much as a volatile solvent, and when such a liquid resin component is used, when heated to cure, the viscosity before curing reaction occurs It is thought that the resin component spreads according to the profile of the copper foil by the capillary phenomenon.

In this regard, according to the second aspect of the present invention, since fine powders such as fine cellulose fibers are dispersed in the resin filler, the reinforcing effect is expressed by the interaction between the fine powders described above, and even when heated at a high temperature. Since the viscosity of is maintained, it is considered that the peculiar effect of curing is preceded before the resin component spreads to the copper foil.

Moreover, according to such a characteristic structure of this invention, in the printed wiring board which has at least one of a recessed part and a through hole, the excess grinding | polishing for smoothing in the grinding | polishing process after hardening of the curable resin composition filled in the recessed part or through hole is carried out. Can exhibit the effect peculiar to this invention that recesses, such as a hole part, do not generate | occur | produce.

Although the detailed mechanism is not clear about the recessed part and recessed part of this grinding | polishing process, since the resin filler is used so that it may be completely filled in the recessed part or through hole, such as a via hole and a through hole, And the upper portion of the through-holes so as to protrude (Fig. 7-4 (a)), and after thermosetting, in the polishing step, unnecessary parts are cut off with a buff roll or the like. However, such a thermosetting resin filler deforms upon application of pressure, so that residual material is likely to occur (Fig. 7-4 (b)). At this time, if the conditions for polishing are severed and the polishing is performed so that no residue is left, the resin filler is excessively shaved, so that a recess is generated in the through hole (FIG. 7-4 (c)).

In this regard, according to the second aspect of the present invention, since fine powders such as fine cellulose fibers are dispersed in the resin filler, the reinforcing effect is expressed by the interaction between the fine powders described above, and the strength of the resin is increased. Therefore, it is thought that the characteristic effect that pressure deformation becomes small and it becomes possible to grind uniformly is acquired.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of the 2nd aspect of this invention is described in detail.

[(A) Fine Powder]

As fine powder used for the 2nd aspect of this invention, the thing similar to what was demonstrated in 1st aspect can be used. By using such fine powder, when the curable resin composition containing such fine powder is used as a resin filler for filling such as a hole, the reinforcing effect is expressed by taking an interaction in which the fine powders attract each other, as described above. Further, expansion after high-temperature heating and spreading of the resin component are hardly generated, and a cured product which hardly generates recesses of the filler filled in the hole or the like even in the polishing step can be formed. In addition, this effect remarkably expresses hydrophilicity among fine powders.

[(B) Thermosetting Component]

Although a thermosetting component is not specifically limited, The compound which has a 2 or more cyclic ether in 1 molecule is preferable. The cyclic ether may be a cyclic thioether. A cyclic ether compound may be used individually by 1 type, and may use 2 or more types together. Among these cyclic ether compounds, an epoxy resin and an oxetane resin are preferable and an epoxy resin is especially preferable.

As said epoxy resin, a well-known epoxy resin can be used. For example, as a thermosetting resin, what is necessary is just resin which hardens by heating and shows electrical insulation, For example, bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol E-type epoxy resin, bisphenol M Novolak-type epoxy resins, such as a bisphenol-type epoxy resin, such as a bisphenol-type epoxy resin, a bisphenol P-type epoxy resin, and a bisphenol Z-type epoxy resin, a bisphenol A novolak-type epoxy resin, a phenol novolak-type epoxy resin, and a cresol novolak epoxy resin, Biphenyl type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl aralkyl type epoxy resin, arylalkylene type epoxy resin, tetraphenylolethane type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin , Norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, Lycidyl methacrylate copolymer type epoxy resin, copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate, epoxy-modified polybutadiene rubber derivative, CTBN modified epoxy resin, trimethylol propane polyglycidyl ether, phenyl- 1,3-diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol poly Glycidyl ether, tris (2,3-epoxypropyl) isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, and the like.

As curable resin composition of this invention, dispersibility of fine powder like fine cellulose fibers can be improved by mixing the epoxy resin which uses amines as a precursor as an epoxy resin. Specifically, when the dispersion of the fine powder is produced, the fluidity is increased and the viscosity can be lowered. Therefore, the workability is improved and the viscosity of the composition is lowered. Therefore, the fine powder is easily mixed or blended with a solvent. can do.

As epoxy resin which uses amines as a precursor, tetraglycidyl diamino diphenylmethane, the glycidyl compound of xylenediamine, the triglycidyl aminophenol, the substituent in each positional isomer of glycidyl aniline, an alkyl group, or halogen Can be mentioned. As a commercial item of tetraglycidyl diamino diphenylmethane, for example, Sumiepoxy ELM434 (made by Sumitomo Chemical Co., Ltd.), Araldite MY720, MY721, MY9512, MY9612, MY9634, MY9663 (Huntsman Advance) Materials, Ltd.) and JER604 (made by Mitsubishi Chemical Corporation) are mentioned. As a commercial item of triglycidyl amino phenol, JER630 (made by Mitsubishi Chemical Corporation), Araldite MY0500, MY0510 (made by Huntsman Advanced Materials Co., Ltd.), ELM100 (made by Sumitomo Chemical Co., Ltd.) ). As a commercial item of glycidyl anilines, GAN and GOT (made by Nippon Kayaku Co., Ltd.) are mentioned, for example.

Moreover, as curable resin composition of this invention, when mixing or mix | blending fine powders, such as a fine cellulose fiber, and making it low viscosity, a heat resistant fall will be seen, and when it mix | blends the component which improves heat resistance in order to improve this, the tendency to become high viscosity arises, The problem associated with a bisphenol-A epoxy resin and a bisphenol-F epoxy resin is used together, and is compounded.

Moreover, since alkylglycidyl ether, such as 1, 6- hexanediol diglycidyl ether, has a low viscosity, it is preferable to use it as a diluent or viscosity adjustment, when the viscosity of a composition is high.

In this invention, you may use other thermosetting resins other than a cyclic ether compound as (B) thermosetting component according to the objective. As thermosetting resins other than a cyclic ether compound, what is necessary is just resin which hardens | cures by heating, For example, novolak-type phenol resins, such as a phenol novolak resin, a cresol novolak resin, bisphenol A novolak resin, an unmodified resol phenol resin Phenol resins such as resol type phenol resins such as oil-modified resol phenol resins modified with oil, linseed oil, walnut oil, triazine ring-containing resins such as phenoxy resin, urea (urea) resin, melamine resin, and unsaturated polyester Resin, bismaleimide resin, diallyl phthalate resin, silicone resin, resin having benzoxazine ring, norbornene-based resin, cyanate resin, isocyanate resin, urethane resin, benzocyclobutene resin, maleimide resin, bismaleimide tree Azine resin, polyazomethine resin, thermosetting polyimide, dicyclopentadienyldiphenol ester compound, bispe A diacetate, diphenyl phthalate, diphenyl terephthalate, terephthalic acid-bis [4- (methoxycarbonyl) phenyl] active ester compound and the like.

(B) It is preferable that the compounding quantity of a thermosetting component is 10-70 mass% with respect to the whole amount of a composition. If it is 10 mass% or more, workability, such as printing, is excellent. If it is 70 mass% or less, it will become low thermal expansion. More preferably, it is 20-60 mass%.

[Curing agent]

It is preferable to use a hardening | curing agent for the curable resin composition of this invention according to the objective.

As a hardening | curing agent of this invention, an imidazole compound can be used, for example. As an imidazole compound, 2-methylimidazole, 4-methyl-2-ethylimidazole, 2-phenylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-, for example Methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, And imidazole derivatives such as 1-cyanoethyl-2-undecylimidazole.

Moreover, the imidazole compound containing a triazine structure can also be mentioned as an imidazole compound. As an imidazole compound containing a triazine structure, 2, 4- diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-S-triazine, 2, 4- diamino-6 -[2'-Methylimidazolyl- (1 ')]-ethyl-S-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl- S-triazine, 2, 4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-S-triazine, etc. are mentioned. Examples of these commercial items include 2MZ-A, 2MZ-AP, 2MZA-PW, C11Z-A, 2E4MZ-A (manufactured by Shikoku Kasei Kogyo Co., Ltd.), and the like.

Among the imidazole compounds, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-S-triazine, 2,4-diamino-6- [2'-ethyl -4'-methylimidazolyl- (1 ')]-ethyl-S-triazine is preferred. Thereby, the storage stability of curable resin composition is excellent, and the hardened | cured material which does not produce a crack in short time hardening is obtained.

As the curing agent, compounds other than imidazole compounds may be used, for example, dicyandiamide and its derivatives, melamine and its derivatives, diaminomaleonitrile and its derivatives, diethylenetriamine, triethylenetetramine, tetramethylene Pentamine, bis (hexamethylene) triamine, triethanolamine, diaminodiphenylmethane, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzyl Amines such as organic acid hydrazides such as amines, 4-methyl-N, N-dimethylbenzylamine, adipic dihydrazide, and dihydrazide sebacic acid, and 1,8-diazabicyclo [5.4.0] undecene-7 , 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, or triphenylphosphine, tricyclohexylphosphine, tributylphosphine, methyldiphenyl You may use organic phosphine compounds, such as a phosphine, a phenol compound. Moreover, as a commercial item, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (made by Shikoku Kasei Kogyo Co., Ltd.), ATU (made by Ajinomoto Co., Ltd.), U-CAT3503N, U-CAT3502T, DBU, DBN, U-CATSA102, U-CAT5002 (made by San Apro Corporation), etc. are mentioned. Dicyandiamide, melamine, acetoguanamine, benzoguanamine, 3,9-bis [2- (3,5-diamino-2,4,6-triazalphenyl) ethyl] -2,4,8, Guanamine and derivatives thereof, such as 10-tetraoxaspiro [5.5] undecane, and organic acid salts and epoxy adducts thereof, are known to have adhesion and rust resistance with copper, and not only act as a curing agent for epoxy resins, It can contribute to preventing discoloration of copper of a printed wiring board.

As said phenolic compound, For example, a phenol novolak resin, an alkylphenol novolak resin, a triazine structure containing novolak resin, bisphenol A novolak resin, a dicyclopentadiene type phenol resin, a xyloxic phenol resin, a copna resin, Known and conventional ones such as phenol compounds such as terpene-modified phenol resins and polyvinyl phenols, naphthalene-based curing agents and fluorene-based curing agents can be used alone or in combination of two or more thereof. As said phenolic compound, HE-610C, 620C by Air Water Corporation, TD-2131, TD-2106, TD-2093, TD-2091, TD-2090, VH-4150, VH by DIC Corporation -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, SN-170, SN180, SN190, SN475, SN485, SN495, SN375, SN395, JX made by Shinnitetsu Sumikin Kagaku Co., Ltd. DPP, Meiwa Kasei Co., Ltd. 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, Mitsui Chemicals Co., Ltd. XL, XLC, RN, RS, RX etc. are mentioned, However, It is not limited to these.

A hardening | curing agent may be used individually by 1 type, and may be used in combination of 2 or more type. The compounding quantity of a hardening | curing agent may be a well-known conventional compounding quantity with respect to a thermosetting component, For example, it is preferable to set it as 0.01-10 mass parts with respect to 100 mass parts of epoxy resins. However, when a hardening | curing agent is a phenol compound, it is preferable to set it as 1-150 mass parts with respect to 100 mass parts of epoxy resins.

[(C) Boric Acid Ester Compound]

Curable resin composition of this invention can contain a boric acid ester compound. Since a boric acid ester compound has the effect | action which improves the storage stability of a resin composition more, it is preferable to use it. The boric acid ester compound is thought to exert such an action by reacting with the surface of the latent curing accelerator and modifying and encapsulating the surface of the latent curing agent. Examples of the boric acid ester compound include trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate and trioctyl Borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris (2-ethylhexyloxy) borane, bis (1,4,7,10-tetraoxoundecyl ) (1,4,7,10,13-pentaoxatetradecyl) (1,4,7-trioxoundecyl) borane, tribenzylborate, triphenylborate, tri-o-tolylborate, tri-m- Tolylborate, triethanolamine borate, and the like. These can be purchased as a reagent. Moreover, as a commercial item, the duct duct L-07N and L-07E (made by Shikoku Kasei Kogyo Co., Ltd.) which are the compound products of an epoxy resin and a phenol novolak resin are mentioned.

A boric acid ester compound may be used individually by 1 type, and may be used in combination of 2 or more type. It is preferable that the compounding quantity of a boric acid ester compound shall be 0.01-3 mass parts with respect to 100 mass parts of thermosetting components. If it is 0.01 mass part or more, storage stability will become favorable. Curability becomes favorable that it is 3 mass parts or less.

[(D) Filler]

Curable resin composition of this invention can contain filler other than said (A) fine powder further. As fillers other than said (A) fine powder, although an organic filler and an inorganic filler can also be used as long as it is a well-known well-known thing according to the required characteristic of the curable resin composition of this invention, it is more preferable to use an inorganic filler.

As an inorganic filler, barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica powder, Neuburg silica, silicon nitride, nitride Aluminum etc. can be mentioned. Among the inorganic fillers, calcium carbonate is preferable.

The shape of the filler includes spherical shape, needle shape, plate shape, flaky shape, hollow shape, indefinite shape, hexagonal shape, cubic shape, flaky shape and the like, but spherical shape is preferable in terms of high filling.

A filler may be used individually by 1 type, and may be used in combination of 2 or more type. The compounding quantity of a filler becomes like this. Preferably it is 10-70 mass% with respect to the whole amount of a composition, More preferably, it is 20-60 mass%. If it is 10 mass% or more, workability, such as printing, is excellent. If it is 70 mass% or less, it will become low thermal expansion.

[Other Ingredients]

In the curable resin composition of this invention, it is not necessary to necessarily use an organic solvent, For the purpose of adjusting the viscosity of a composition, etc., you may add the organic solvent so that a void does not generate | occur | produce.

Furthermore, in the curable resin composition of this invention, well-known conventional coloring agents, such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black, are stored as needed. In order to impart storage stability, known conventional thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, tert-butyl catechol, pyrogallol, phenothiazine, and the like, and conventional known polymers such as clay, kaolin, organic bentonite and montmorillonite Known commonly used agents such as thickeners or thixotropic agents, antifoaming agents and / or leveling agents such as silicone, fluorine and polymers, imidazole, thiazole, triazole and silane coupling agents, photopolymerization initiators, dispersants and flame retardants Additives can be mix | blended.

The curable resin composition of the present invention may be either one-component or two-component or more.

The curable resin composition of this invention obtained as mentioned above is easily used by the hole part, such as a via hole and a through hole, of a printed wiring board using the method conventionally used, for example, the screen printing method, the roll coating method, the die coating method, etc. It can be charged.

For this reason, it is preferable that the viscosity of curable resin composition of this invention exists in the range of 100-1000 dPa * s, and 200-900 dPa * s, especially 300-800 dPa * s at 25 +/- 1 degreeC. By setting it as such a range, filling of a hole part can be filled easily in a recessed part and a through hole easily without generation | occurrence | production of a void etc ..

Moreover, it is preferable that it is 150 degreeC or more, and, as for the glass transition temperature (Tg) of curable resin composition of this invention, it is more preferable that it is 160 degreeC or more. When Tg is 150 degreeC or more, generation | occurrence | production of a delamination can be suppressed.

The cured product of the present invention is obtained by curing the curable resin composition of the second aspect of the present invention.

In the printed wiring board of the present invention, at least one of the recess and the through hole is filled with a cured product of the curable resin composition of the second aspect of the present invention.

Hereinafter, an example of the manufacturing method of the printed wiring board which fills the curable resin composition of this invention into recesses and through holes, such as a via hole and a through hole provided in the wiring board, and forms a pad or wiring thereon, is explained with reference to FIG. 7-1. do.

(1) hole filling

First, the through hole 103 (core) provided in the wiring board 101 in which the through hole 103 and the conductor circuit layer 104 are formed in the base material 102 as shown in Fig. 7-1 (a). When using a multilayer printed wiring board as a base material, in addition to a through hole, the curable resin composition of this invention is filled into recesses, such as a via hole, as shown to FIG. 7-1 (b). For example, a mask provided with an opening in the through hole portion is mounted on a substrate and filled in the through hole by a printing method or a dot printing method.

Here, as the wiring board 101, the base material, such as the glass epoxy base material which laminated the copper foil, or the polyimide resin base material, the resin base materials, such as a bismaleimide-triazine resin base material, the fluororesin base material, a ceramic base material, a metal base material ( Drilled through holes in 102, electroless plating or further electroplating on the wall surface and copper foil surface of the through holes, and the through hole 103 and the conductor circuit layer 104 were suitably used. Can be. Copper plating is generally used as plating.

(2) polishing

Next, the filled curable resin composition is heated at about 90 to 130 ° C. for about 30 to 90 minutes to be precured. Since the hardness of the hardened | cured material 105 preliminarily hardened | cured in this way is comparatively low, the unnecessary part protruding from the surface of a board | substrate can be easily removed by physical polishing, and it can be set as a flat surface. Then, it heats again at about 140-180 degreeC for about 30 to 90 minutes, and hardens | cures it (finish hardening).

In addition, the "preliminary hardening" or "preliminary hardened | cured material" said here generally means that the reaction rate of epoxy is a state of 80%-97%. In addition, the hardness of the said precured material can be controlled by changing the heating time and heating temperature of precure. Thereafter, as shown in Fig. 7-1 (c), the unnecessary portion of the main hardened product 105 protruding from the through hole is removed by polishing to planarize. Polishing can be performed by belt sander, buff polishing, or the like.

(3) Formation of Conductor Circuit Layer

A plating film is formed on the surface of the substrate through which the through holes are filled, as shown in Fig. 7-1 (d). Thereafter, an etching resist is formed, and the resist non-forming portion is etched (not shown). Subsequently, the etching resist is peeled off to form the conductor circuit layer 106 as shown in Fig. 7E.

As explained above, the curable resin composition of this invention is a through-hole resin filler provided in the printed wiring board as shown in FIG. 7-1, Furthermore, it is a multilayer printed wiring board as shown in FIG. 7-2 or FIG. 7-3. Although it can use suitably as a resin filler of the through hole and via hole provided in this, it is not limited to these uses, For example, it can be used also for uses, such as a sealing material.

Example

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail using an Example.

<First Embodiment>

[Production of Fibrous Fine Cellulose Powder]

Preparation Example 1 (CNF1)

After bleaching kraft pulp fiber (Machenzie CSF 650 ml by Fletcher Challenge Canada) of coniferous tree with agitation with 9900 g of ion-exchanged water, TEMPO (2,2,6,6-tetramethylpiperier made by ALDRICH) 1.25 mass% of din1-oxyl free radicals), 12.5 mass% of sodium bromide, and 28.4 mass% of sodium hypochlorite were added in this order. A pH stat was used and 0.5 M sodium hydroxide was added dropwise to maintain the pH at 10.5. After 120 minutes (20 degreeC) of reaction, dripping of sodium hydroxide was stopped and the oxidation pulp was obtained. Oxidized pulp obtained using ion-exchanged water was sufficiently washed and then dewatered. Thereafter, 3.9 g of oxidized pulp and 296.1 g of ion-exchanged water were subjected to two micronization treatments at 245 MPa using a high-pressure homogenizer (manufactured by Sugino Machine Co., Ltd., Starburst Laboratory HJP-2 5005) to form carboxyl group-containing fine cellulose. The dispersion liquid (solid content concentration 1.3 mass%) of the powder was obtained.

Subsequently, 4088.75 g of the dispersion liquid of the obtained carboxyl group-containing fine cellulose powder was put into a beaker, 4085 g of ion-exchanged water was added to make a 0.5 mass% aqueous solution, and it stirred at room temperature (25 degreeC) with a mechanical stirrer for 30 minutes. Subsequently, 245g of 1M aqueous hydrochloric acid solution was added and reacted at room temperature for 1 hour. After completion of the reaction, the solution was reprecipitated with acetone, filtered, and then washed with acetone / ion exchanged water to remove hydrochloric acid and salt. Finally, acetone was added and filtered to obtain a dispersion (solid content concentration of 5.0% by mass) of acetone-containing acidic cellulose powder in a state where the carboxyl group-containing fine cellulose powder was swollen in acetone. After the reaction was completed, the mixture was filtered, and then washed with ion-exchanged water to remove hydrochloric acid and salt. After solvent substitution with acetone, solvent substitution was carried out with DMF to obtain a dispersion (average fiber diameter of 3.3 nm, solid content concentration of 5.0% by mass) of the DMF-containing acidic cellulose powder in a state where the carboxyl group-containing fine cellulose powder was swollen.

Preparation Example 2 (CNF2)

40 g of the dispersion liquid of DMF-containing acid cellulose powder obtained in Production Example 1 and 0.3 g of hexylamine were placed in a beaker equipped with a magnetic stirrer and a stirrer, and dissolved in 300 g of ethanol. The reaction solution was reacted at room temperature (25 ° C) for 6 hours. After completion | finish of reaction, it filtered and wash | cleaned and solvent-substituted with DMF, and obtained the dispersion liquid (solid content concentration 5.0 mass%) of the fine cellulose powder by which the amine was connected to the fine cellulose powder through an ionic bond.

The CNF 2 produced by the method of Production Example 2 has particularly good dispersibility, and can be dispersed by a general method without using a special disperser such as a high pressure homogenizer.

Preparation Example 3 (CNF3)

10 mass% of fibrous fine cellulose powders (BiFi-s by Sugino Machine Co., Ltd., 80 nm of average fiber diameters) were dehydrated and filtered, 10 times the amount of carbitol acetate of the mass of a filtrate was added, and it filtered, after stirring for 30 minutes. This substitution operation was repeated 3 times, 20 times the amount of carbitol acetate of the filtrate mass was added, and the dispersion liquid (solid content concentration 5.0 mass%) of the fine cellulose powder was produced.

[Production of Cellulose Nanocrystal Particles]

Preparation Example 4 (CNC1)

The portrait sheets of dried coniferous bleached kraft pulp were treated with a cutter mill and a pin mill to obtain a cotton fiber. 100 g of this cotton fiber was taken as an absolute dry mass, suspended in 2 L of 64% sulfuric acid aqueous solution, and hydrolyzed at 45 degreeC for 45 minutes.

After the obtained suspension was filtered, 10 L of ion-exchanged water was injected, stirred and uniformly dispersed to obtain a dispersion. Subsequently, the process of filtration dehydration was repeated 3 times with respect to the said dispersion liquid, and the dehydration sheet was obtained. Subsequently, the obtained dehydration sheet was diluted with 10 L of ion-exchanged water, the aqueous solution of 1N sodium hydroxide was added little by little, stirring, and it was set as about pH12. Then, this suspension was filtered and dewatered, 10 L of ion-exchange water was added, and the process of stirring and filtering and dehydrating was repeated twice.

Subsequently, ion-exchanged water was added to the obtained dewatering sheet to prepare a 2% suspension. This suspension was passed 10 times by the pressure of 245 MPa with the wet granulation apparatus ("Altimizer" by Sugino Machine Co., Ltd.), and the cellulose nanocrystal particle aqueous dispersion was obtained.

Thereafter, the solvent was substituted with acetone, followed by solvent substitution with DMF to obtain a DMF dispersion (solid content concentration of 5.0% by mass) in a state in which the cellulose nanocrystal particles were swollen. As a result of observing and measuring the cellulose nanocrystal particle in the obtained dispersion liquid by AFM, the average crystal width was 10 nm and the average crystal length was 200 nm.

Preparation Example 5 (CNC2)

Except having changed the cellulose raw material of manufacture example 4 into cotton wool (made by Hakujuji company), it manufactured by the same method, and obtained the DMF dispersion liquid (solid content concentration 5.0 mass%) of the swelled cellulose nanocrystal particle. As a result of observing and measuring the cellulose nanocrystal particle in the obtained dispersion liquid by AFM, the average crystal width was 7 nm and the average crystal length was 150 nm.

(Examples 1-1 to 1-15, Comparative Examples 1-1 to 1-8)

After mixing and stirring each component according to the description in Tables 1 to 3 below, each composition was prepared by repeatedly dispersing six times using a high pressure homogenizer Nanovater NVL-ES008 manufactured by Yoshida Kikai Kogyo Co., Ltd. In addition, the numerical value of Tables 1-3 shows a mass part.

About each composition obtained by the Example and the comparative example, thermal expansion rate, solder heat resistance, insulation, and toughness (elongation rate) were evaluated. The evaluation method is as follows.

[Coefficient of Thermal Expansion]

Each composition was apply | coated to the PET film with a thickness of 38 micrometers with the applicator of a gap of 120 micrometers, and it dried at 90 degreeC for 10 minutes with the hot air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Then, it crimped | bonded for 60 second on 60 degreeC and the pressure of 0.5 MPa on the copper foil of thickness 18micrometer with a vacuum laminator, laminated the resin layer of each composition, and peeled off the PET film. Subsequently, it heated in 180 degreeC for 30 minutes in the hot air circulation type drying furnace, hardened | cured, and peeled from copper foil, and obtained the film sample containing the hardened | cured material of each composition. The obtained film sample was cut into 3 mm width x 30 mm length, and it was set as the test piece for thermal expansion coefficient measurement. About this test piece, using TMA (Thermomechanical Analysis) Q400 made by T-A Instruments Inc., the temperature was increased to 5 ° C./min to 20 to 250 ° C. under a tensile mode of 16 mm, a load of 30 mN, and a nitrogen atmosphere, followed by 250 It cooled to 5 degree-C / min to -20 degreeC, and thermal expansion coefficient (alpha) 1 and (alpha) 2 (ppm / K) were measured. These measurement results are shown together in Tables 1-3.

[Solder heat resistance]

Each composition is applied to the entire surface of the FR-4 copper clad laminate having a size of 150 mm x 95 mm and 1.6 mm by 80 mesh Tetron bias plate screen printing, dried at 80 ° C. for 30 minutes in a hot air circulation drying furnace, and then at 180 ° C. It heat-hardened for 30 minutes and obtained the test board | substrate which formed the resin layer containing the hardened | cured material of each composition. The rosin flux was apply | coated to the resin layer surface of this test board | substrate, it flowed into the 260 degreeC solder layer for 60 second, and it washed with propylene glycol monomethyl ether acetate, and then ethanol. About the test board | substrate after washing, swelling, peeling of a resin layer, and the change of the surface state were observed visually, and solder heat resistance was evaluated. Evaluation criteria were made into (circle) what the abnormality by swelling, peeling, surface melt | dissolution, softening, etc. are seen by the resin layer, and what is invisible is (circle). These evaluation results are shown together in Tables 1-3.

[Insulation]

Each composition was apply | coated to the PET film with a thickness of 38 micrometers with the applicator of a gap of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Subsequently, each composition was pressed for 60 seconds under a condition of 60 ° C. and a pressure of 0.5 MPa using a vacuum laminator on an A coupon of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm thick FR-4 substrate with a thickness of 35 μm copper. The resin layer was laminated, the PET film was peeled off, and heated at 180 ° C. for 30 minutes in a hot air circulation drying furnace to cure. Subsequently, the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 was cut to form an electrically independent terminal (cut at the dotted line in Figs. 1-4). And the bias of DC500V was applied so that the upper part of A coupon might be a cathode and the lower part was an anode, and insulation resistance value was measured and evaluated.

(Circle) evaluation and the thing of insulation resistance value less than 100 G (ohm) made x into evaluation criteria. These evaluation results are shown together in Tables 1-3.

[tenacity]

Each composition was apply | coated to the PET film of thickness 38micrometer with the applicator of 200 micrometers, and it dried for 20 minutes at 90 degreeC in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Subsequently, an electrolytic copper foil having a thickness of 18 μm with the gloss side upward was fixed with a tape on a FR-4 copper clad laminate having a thickness of 1.6 mm, and the dry film was 60 ° C. under a vacuum laminator at 60 ° C. under a pressure of 0.5 MPa. The resin layer of each composition was laminated on the said electrolytic copper foil, then PET film was peeled, and it heated at 180 degreeC for 30 minutes in the hot-air circulation type drying furnace, and hardened the resin layer. And the fixed tape was peeled off, the electrolytic copper foil was peeled off, and the film sample containing a resin layer was obtained. Next, in accordance with JIS K7127, the film sample was cut to a predetermined size to prepare a test piece for evaluation. About this test piece, the stress [MPa] and the distortion [%] were measured at 10 mm / min of tensile velocity using the small benchtop testing machine EZ-SX by Shimadzu Corporation. Distortion [%] at this time is the elongation rate at the time of breaking a test piece, and since it can be evaluated that toughness is so large that it is high, toughness was evaluated from this distortion [%].

As for evaluation criteria, what made distortion [%] less than 2.0% x and what was 2.0% or more (circle). These evaluation results are shown together in Tables 1-3.

* 1-1) Thermosetting resin 1-1: Cyclohexanone varnish (cyclic ether compound which has naphthalene frame | skeleton) of 50 mass% of solid content of epiclon HP-4032 DIC Corporation

* 1-2) Thermosetting resin 1-2: cyclohexanone varnish (cyclic ether compound which has naphthalene frame | skeleton) of 50 mass% of solid content by NC-7300L Nippon Kayaku Co., Ltd.

* 1-3) Thermosetting resin 1-3: Cyclohexanone varnish (cyclic ether compound which has an anthracene skeleton) of 50 mass% of solid content of YX-8800 Mitsubishi Chemical Corporation

* 1-4) Thermosetting resin 1-4: Cyclohexanone varnish (cyclic ether compound which has a dicyclopentadiene skeleton) of 50 mass% of epiclonal HP-7200 solid content

* 1-5) Thermosetting resin 1-5: Cyclohexanone varnish (cyclic ether compound which has a biphenyl skeleton) of 50 mass% of solid content made by NC-3000H Nippon Kayaku Co., Ltd.

* 1-6) Thermosetting resin 1-6: Cyclohexanone varnish (cyclic ether compound which has a biphenyl skeleton) of 50 mass% of solid content by YX-4000 Mitsubishi Chemical Corporation

* 1-7) Thermosetting resin 1-7: cyclohexanone varnish of 50 mass% of solid content made by Epiclone N-740 DIC Co., Ltd.

* 1-8) Thermosetting resin 1-8: Epiclone 830 DIC Corporation

* 1-9) Thermosetting resin 1-9: manufactured by JER827 Mitsubishi Chemical Corporation

* 1-10) Phenoxy resin 1-1: YX6954 cyclohexanone varnish of 30 mass% of solid content by Mitsubishi Chemical Corporation

* 1-11) Curing agent 1-1: 60 mass% cyclohexanone varnish by HF-1 Maya and Kasei Corporation

* 1-12) Curing agent 1-2: Bisphenol A diacetate Tokyo Kasei Kogyo Co., Ltd. agent (active ester)

* 1-13) Curing catalyst 1-1: 2E4MZ (2-ethyl-4-methylimidazole) manufactured by Shikoku Kasei Kogyo Co., Ltd.

* 1-14) Filler 1-1: Admafine SO-C2 Co., Ltd.

* 1-15) Organic Solvent 1-1: Dimethylformamide

* 1-16) Antifoaming agent 1-1: made by BYK-352 Big Chemie Japan Co., Ltd.

* 1-17) Filler 1-2: B-30 barium sulfate manufactured by Sakai Kagaku Kogyo Co., Ltd.

* 1-18) Filler 1-3: DAW-07 Alumina manufactured by Denka Corporation

* 1-19) Dispersant 1-1: manufactured by DISPERBYK-111 Big Chemistry

As apparent from the results shown in Tables 1 to 3, by using the fine cellulose powder and fillers other than the fine cellulose powder in combination, low thermal expansion coefficient can be maintained not only at normal temperature but also at a high temperature region during component mounting, It was confirmed that the cured product excellent in various properties of can be obtained. Moreover, it was confirmed from the evaluation result of solder heat resistance that each composition of the Example was excellent in heat resistance and chemical-resistance, and can be used as a composition for wiring boards. In addition, it was confirmed that the relative dielectric constant and dielectric loss tangent were reduced by using an active ester as a curing agent.

Second Embodiment

As the fine cellulose fibers CNF1 to CNF3 and the cellulose nanocrystal particles CNC1 and CNC2, the same production examples 1 to 5 as those of the first embodiment were used.

Synthesis Example 1 (varnish 1)

In a 2-liter separable flask equipped with a stirrer, a thermometer, a reflux cooler, a dropping funnel and a nitrogen introduction tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate as a polymerization initiator (Nichi Oil ( 21.4 g of the main agent, brand name, perbutyl O) were added, and it heated at 90 degreeC. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (manufactured by Daicel Co., Ltd., trade name; Flaccel FM1) were added to Bis (which is a polymerization initiator). It was added dropwise over 3 hours with 21.4 g of 4-t-butylcyclohexyl) peroxydicarbonate (manufactured by Nichi Oil Co., Ltd., trade name; perroyl TCP). Moreover, the carboxyl group-containing copolymer resin was obtained by aged this for 6 hours. In addition, these reactions were performed in nitrogen atmosphere.

Next, 363.9 g of 3,4-epoxycyclohexyl methyl acrylate (made by Daicel, brand name; cyclomer A200), 3.6 g of dimethylbenzylamine as a ring-opening catalyst, and hydroquinone mono as a polymerization inhibitor are obtained to the obtained carboxyl group-containing copolymerization resin. The ring-opening addition reaction of epoxy was performed by adding 1.80g of methyl ether, heating at 100 degreeC, and stirring this. After 16 hours, a solution containing 53.8% by mass (nonvolatile matter) of a carboxyl group-containing resin having an acid value of 108.9 mgKOH / g and a mass average molecular weight of 25,000 was obtained.

Synthesis Example 2 (Varnish 2)

To a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, diethylene glycol monoethyl ether acetate as a solvent and azobisisobutyronitrile as a catalyst were added and heated to 80 ° C. under a nitrogen atmosphere, The monomer which mixed methyl methacrylate in the molar ratio of 0.40: 0.60 was dripped over about 2 hours. Furthermore, after stirring this for 1 hour, the temperature was raised to 115 degreeC, it deactivated, and the resin solution was obtained.

After cooling this resin solution, it uses tetrabutylammonium bromide as a catalyst and add-reacts butylglycidyl ether at the molar ratio of 0.40 with equivalence of the carboxyl group of obtained resin on the conditions of 30 hours at 95-105 degreeC, Cooled.

Moreover, tetrahydrophthalic anhydride was addition-reacted at the molar ratio of 0.26 with the conditions of 8 hours at 95-105 degreeC with respect to the OH group of resin obtained above. This was taken out after cooling, and the solution containing 50 mass% (non-volatile content) of carboxyl group-containing resin whose acid value of solid content is 78.1 mgKOH / g and mass average molecular weight is 35,000.

Synthesis Example 3 (Varnish 3)

To a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, 210 g of cresol novolac type epoxy resin (manufactured by DIC Corporation, Epiclone N-680, epoxy equivalent = 210) and 96.4 g of carbitol acetate as a solvent were added. It was added and dissolved by heating. Next, 0.1 g of hydroquinone as a polymerization inhibitor and 2.0 g of triphenylphosphine as a reaction catalyst were added thereto. The mixture was heated to 95 to 105 ° C, 72 g of acrylic acid was slowly added dropwise, and reacted for about 16 hours until the acid value became 3.0 mgKOH / g or less. After cooling this reaction product to 80-90 degreeC, 76.1g of tetrahydrophthalic anhydrides were added, and it reacted for about 6 hours until the absorption peak (1780cm <^-1> ) of acid anhydrides disappeared by infrared absorption analysis. 96.4g of aromatic solvent ifsol # 150 of Idemitsu Kosan Co., Ltd. product was added to this reaction solution, and it took out after diluting. Thus, the obtained carboxyl group-containing photosensitive polymer solution was 65 mass% of non volatile matters, and the acid value of solid content was 78 mgKOH / g.

After mixing and stirring each component according to the description of following Tables 4-12, it disperse | distributed 6 times using the high-pressure homogenizer Nanovater NVL-ES008 of Yoshida Kikai Kogyo Co., Ltd., and each composition was manufactured. In addition, the numerical value of Tables 4-12 shows a mass part.

[Interlayer Insulation Reliability]

(Thermosetting composition)

Each composition shown in Tables 4-6 was apply | coated to the PET film with a thickness of 38 micrometers with the applicator of a gap of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Thereafter, the A coupon image of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm thick FR-4 substrate having a thickness of 35 μm (part shown by arrows in Fig. 2-2: right side of the comb pattern at the bottom of the figure). The resin layer of each composition was laminated | stacked for 60 second on 60 degreeC and the pressure of 0.5 MPa by the vacuum laminator, and PET film was peeled off, and it heated and hardened | cured by heating 180 degreeC for 30 minutes in a hot-air circulation type drying furnace. Subsequently, permanganic acid desmear (manufactured by ATOTECH), electroless copper plating (through cup PEA, manufactured by Uemura Kogyo Co., Ltd.), and electrolytic copper plating were processed in order, and copper plating having a copper thickness of 25 µm was performed. Subsequently, an annealing treatment was performed at 190 ° C. for 60 minutes in a hot air circulation drying furnace to obtain a test substrate subjected to copper plating treatment. And the acid resistant tape shape | molded by the circle of 1 cm in diameter was stuck on copper plating so that it might become the center of A coupon, and 40 degreeC 40 mass% ferric chloride aqueous solution removed copper plating other than the acid resistant tape part on resin hardened | cured material by etching. . In the test board | substrate at this time, the hardened | cured material of each composition is formed as a coating film on the A coupon of IPC MULTI-PURPOSE TEST BOARD B-25, and the circular copper plating of diameter 1cm is formed on it (FIG. 2-3 shows Reference). Subsequently, a wire is attached to the round copper plating with a thread solder and a soldering iron, and a wire is similarly attached to the wiring of the IPC MULTI-PURPOSE TEST BOARD. The test of 200 hours was done in 85% of environments. Ten test pieces were produced about each composition. At this time, insulation resistance was measured at all times, and was made into NG at the time when it became 1x10 <^{6> (} ohm) or less. ?, 1 to 4 NG,?, 5 to 9 NG,?, And 1 to NG were evaluated. The evaluation results are shown in Tables 4 to 6.

(Photocurable thermosetting composition)

Each composition shown in Tables 7-12 was apply | coated to the PET film with a thickness of 38 micrometers with the applicator of a gap of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Subsequently, each composition was pressed for 60 seconds under a condition of 60 ° C. and a pressure of 0.5 MPa using a vacuum laminator on an A coupon of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm thick FR-4 substrate with a thickness of 35 μm copper. The resin layer was laminated, and the entire surface was exposed to 700 mJ / cm ² using a metal halide lamp exposure machine for a printed wiring board, and then the PET film was peeled off, using a developer solution of 1 wt% Na ₂ CO ₃ at 30 ° C. for 60 seconds using a developer. Developed. Then, it hardened | cured by heating 150 degreeC 60 minutes in a hot air circulation type drying furnace. Subsequently, permanganic acid desmear (manufactured by ATOTECH), electroless copper plating (through cup PEA, manufactured by Uemura Kogyo Co., Ltd.), and electrolytic copper plating were processed in order, and copper plating having a copper thickness of 25 µm was performed. Subsequently, an annealing treatment was performed at 190 ° C. for 60 minutes in a hot air circulation drying furnace to obtain a test substrate subjected to copper plating treatment. And the acid resistant tape shape | molded by the circle of diameter 1cm was stuck on copper plating so that it might become the center of A coupon, and copper plating other than the acid resistant tape part on resin hardened | cured material was removed by etching with 40 degreeC 40 mass% ferric chloride aqueous solution. Subsequently, a wire is attached to the round copper plating with a thread solder and a soldering iron, and a wire is similarly attached to the wiring of the IPC MULTI-PURPOSE TEST BOARD. The test of 200 hours was done in 85% of environments. Ten test pieces were produced about each composition. At this time, insulation resistance was measured at all times and was made into NG at the time when it became 1x10 <^{6> (} ohm) or less. ?, 1 to 4 NG,?, 5 to 9 NG,?, And 1 to 4 total NG were evaluated. The evaluation results are shown in Tables 7 to 12.

[Comb electrode insulation reliability]

(Thermosetting composition)

Each composition shown in Tables 4-6 was apply | coated to the PET film with a thickness of 38 micrometers with the applicator of a gap of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Subsequently, each composition was pressed for 60 seconds under a condition of 60 ° C. and a pressure of 0.5 MPa using a vacuum laminator on an A coupon of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm thick FR-4 substrate with a thickness of 35 μm copper. The resin layer was laminated, the PET film was peeled off, and heated at 180 ° C. for 30 minutes in a hot air circulation drying furnace to cure. Subsequently, the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 was cut to form an electrically independent terminal (cut at the dotted line in Figs. 2-4). And the voltage of 50V was applied so that the upper part of A coupon might be a cathode, and the lower part was a positive electrode, and the test for 200 hours was done in 130 degreeC 85% environment. Ten test pieces were produced about each composition. At this time, insulation resistance was measured at all times, and was made into NG at the time when it became 1x10 <^{6> (} ohm) or less. ?, 1 to 4 NG,?, 5 to 9 NG,?, And 1 to NG were evaluated. The evaluation results are shown in Tables 4 to 6.

(Photocurable thermosetting composition)

Each composition shown in Tables 7-12 was apply | coated to the PET film with a thickness of 38 micrometers with the applicator of a gap of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Subsequently, each composition was pressed for 60 seconds under a condition of 60 ° C. and a pressure of 0.5 MPa using a vacuum laminator on an A coupon of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm thick FR-4 substrate with a thickness of 35 μm copper. The resin layer was laminated, and the entire surface was exposed to 700 mJ / cm ² using a metal halide lamp exposure machine for a printed wiring board, and then the PET film was peeled off, using a developer solution of 1 wt% Na ₂ CO ₃ at 30 ° C. for 60 seconds using a developer. Developed. Then, it hardened | cured by heating 150 degreeC 60 minutes in a hot air circulation type drying furnace. Subsequently, the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 was cut to form an electrically independent terminal. And the voltage of 50V was applied so that the upper part of A coupon might become a cathode, and the lower part became an anode, and the test of 200 hours was performed in 130 degreeC 85% environment. Ten test pieces were produced about each composition. At this time, insulation resistance was measured at all times, and was made into NG at the time when it became 1x10 <^{6> (} ohm) or less. ?, 1 to 4 NG,?, 5 to 9 NG,?, And 1 to NG were evaluated. The evaluation results are shown in Tables 7 to 12.

[Solder heat resistance]

(Thermosetting composition)

In a 150 mm × 95 mm, 1.6 mm thick FR-4 copper clad laminate, each composition was formed into a full-side solid pattern by 80 mesh Tetron bias plate screen printing, and dried in a hot air circulation drying furnace for 30 minutes at 80 ° C., followed by 180 It heated and hardened 30 degreeC, and obtained the test piece. The rosin type flux was apply | coated to the hardened | cured material side of the composition of this test piece, it flowed into the 260 degreeC solder layer for 60 second, and it wash | cleaned with propylene glycol monomethyl ether acetate, and then it wash | cleaned with ethanol. About the test piece, swelling and peeling of the coating film, and the change of the surface state were observed visually. The thing which showed abnormality by swelling and peeling, surface melt | dissolution, softening, etc. in a coating film was evaluated as (circle) and what was not seen. The evaluation results are shown in Tables 4 to 6.

(Photocurable thermosetting composition)

Each composition is formed into a full-side solid pattern by 80 mesh Tetron bias plate screen printing on a FR-4 copper clad laminate having a size of 150 mm x 95 mm and 1.6 mm, dried at 80 ° C. for 30 minutes in a hot air circulation drying furnace, and a printed wiring board. for a metal halide to whole surface exposure to 700mJ / cm ² as a light exposure device, and the use of 30 ℃ 1wt% Na ₂ CO ₃ in a developing solution, and then developed for 60 seconds in the developing cartridge. Then, it heat-hardened 150 degreeC 60 minutes in the hot-air circulation type drying furnace, and obtained the test piece. The rosin type flux was apply | coated to the hardened | cured material side of the composition of this test piece, it flowed into the 260 degreeC solder layer for 60 second, and it wash | cleaned with propylene glycol monomethyl ether acetate, and then it wash | cleaned with ethanol. The test piece was visually observed to observe the swelling and peeling of the coating film and the change of the surface state. The thing which showed abnormality by swelling and peeling, surface melt | dissolution, softening, etc. in a coating film was evaluated as (circle) and what was not seen. The evaluation results are shown in Tables 7 to 12.

[Production of Sample for Thermal Expansion Measurement]

(Thermosetting Resin Composition)

Each composition shown in Tables 4-6 was apply | coated to the PET film with a thickness of 38 micrometers with the applicator of a gap of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Then, it crimped | bonded for 60 second on 60 degreeC and the pressure of 0.5 MPa on the copper foil of thickness 18micrometer with a vacuum laminator, laminated the resin layer of each composition, and peeled off the PET film. Next, it heated and hardened | cured by 180 degreeC 30 minutes in a hot-air circulation type drying furnace, peeled copper foil, and obtained the sample of the cured film.

(Photocurable thermosetting resin composition)

A copper foil having a thickness of 18 μm was applied to a FR-4 copper clad laminate having a thickness of 1.6 mm, and each composition shown in Tables 7 to 12 was applied with an applicator having a gap of 120 μm, and dried at 90 ° C. for 10 minutes in a hot air circulation drying furnace. Then, the negative mask with a pattern of 3 mm width x 30 mm length was stuck, and it exposed at 700 mJ / cm <^2> with the metal halide lamp exposure machine for printed wiring boards. Then, using a 30 ℃ 1wt% Na ₂ CO ₃ in a developing solution, and then developed for 60 seconds in the developing cartridge. Then, it heated and hardened | cured by 150 degreeC 60 minutes in a hot air circulation type drying furnace, peeled copper foil, and obtained the sample of the cured film.

[Measurement of thermal expansion rate]

(Thermosetting Resin Composition)

The produced thermal expansion sample was cut into 3 mm width x 30 mm length. This test piece was heated to 5 ° C./min to 20 to 250 ° C. under a tension mode of 16 mm, a load of 30 mN, and a nitrogen atmosphere in a tensioning mode using TMA (Thermomechanical Analysis) Q400 manufactured by T-A Instruments Inc., and then 250 It measured by reducing by 5 degree-C / min to -20 degreeC. The average thermal expansion coefficient (alpha) 1 of 30 degreeC-100 degreeC at the time of temperature fall, and the average thermal expansion coefficient (alpha) 2 of 200 degreeC-230 degreeC were calculated | required. The results are shown in Tables 4 to 6.

(Photocurable thermosetting resin composition)

Except having used the produced sample as it was, it carried out by the method similar to a thermosetting resin composition. The results are shown in Tables 7 to 12.

* 2-1) Thermosetting resin 2-1: Cyclohexanone varnish (cyclic ether compound having a naphthalene skeleton) of 50 mass% of solid content of Epiclone HP-4032 DIC Corporation

* 2-2) Thermosetting resin 2-2: Cyclohexanone varnish (cyclic ether compound having a naphthalene skeleton) of 50 mass% of solid content made by NC-7300L Nippon Kayaku Co., Ltd.

* 2-3) Thermosetting resin 2-3: Cyclohexanone varnish (cyclic ether compound which has an anthracene frame | skeleton) of 50 mass% of solid content by YX-8800 Mitsubishi Chemical Corporation

* 2-4) Thermosetting resin 2-4: Cyclohexanone varnish of 50 mass% of solid content made by Epiclone N-740 DIC Co., Ltd.

* 2-5) Thermosetting resin 2-5: Epiclon 830 DIC Corporation

* 2-6) Thermosetting resin 2-6: made by JER827 Mitsubishi Chemical Corporation

* 2-7) Thermosetting resin 2-7: 60 mass% cyclohexanone varnish by HF-1 Meiwa Kasei Co., Ltd. solid content

* 2-8) Curing catalyst 2-1: 2E4MZ (2-ethyl-4-methylimidazole) manufactured by Shikoku Kasei Kogyo Co., Ltd.

2-9) Filler 2-1: Admafine SO-C2 (Adlicax Co., Ltd.) (Silica)

* 2-10) Organic Solvent 2-1: Dimethylformamide

* 2-11) defoaming agent 2-1: BYK-352 big Chemi Japan Co., Ltd. product

* 2-18) Filler 2-2: B-30 barium sulfate manufactured by Sakai Kagaku Kogyo Co., Ltd.

* 2-19) Filler 2-3: DAW-07 Alumina manufactured by Denka Corporation

* 2-20) Dispersant 2-1: manufactured by DISPERBYK-111 Big Chemistry

* 2-12) Curing catalyst 2-2: Pulverized melamine Nissan Chemical Industries, Ltd.

* 2-13) Curing Catalyst 2-3: Dicyandiamide

* 2-14) Photopolymerization Initiator 2-1: Irgacure 907 manufactured by BASF Corporation

* 2-15) Photocurable resin 2-1: dipentaerythritol tetraacrylate

* 2-16) Thermosetting resin 2-8: TEPIC-H (triglycidyl isocyanurate) manufactured by Nissan Chemical Industries, Ltd.

* 2-17) Colorant 2-1: Phthalocyanine Blue

As apparent from the results shown in Tables 4 to 12, by containing fine powder such as fine cellulose fibers and at least one cyclic ether compound having at least one of a naphthalene skeleton and an anthracene skeleton, insulation reliability between layers and electrodes In particular, it was confirmed that the curable resin composition having excellent insulation reliability between layers and having a low thermal expansion coefficient was obtained. Moreover, it was confirmed from the evaluation result of solder heat resistance that each composition of the Example was excellent in heat resistance and chemical-resistance, and can be used as a composition for wiring boards.

Third Embodiment

As the fine cellulose fibers CNF1 to CNF3 and the cellulose nanocrystal particles CNC1 and CNC2, the same production examples 1 to 5 as those of the first embodiment were used, and as varnishes 1 to varnish 3, the synthesis example 1 similar to the second embodiment was used. 3 to 3 were used.

According to the description of the following Tables 13-21, after mixing and stirring each component, it was made to disperse | distribute 6 times repeatedly using the high-pressure homogenizer Nanovater NVL-ES008 of Yoshida Kikai Kogyo Co., Ltd., and each composition was manufactured. In addition, the numerical value of Tables 13-21 shows a mass part.

[Peel Strength of Plating Copper]

(Thermosetting composition)

Each composition shown in Tables 13-15 was apply | coated to the PET film of thickness 38micrometer with the applicator of gap 120micrometer, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Subsequently, the resin layer of each composition was laminated by pressing the FR-4 copper clad laminate (copper thickness 18 µm) having a size of 150 mm x 100 mm for 60 seconds with a vacuum laminator under a condition of 60 ° C and a pressure of 0.5 MPa, The PET film was peeled off and cured by heating 180 ° C. for 30 minutes in a hot air circulation drying furnace. Subsequently, permanganic acid desmear (manufactured by ATOTECH Co., Ltd.), electroless copper plating (through cup PEA, manufactured by Uemura Kogyo Co., Ltd.), and electrolytic copper plating treatment were performed in this order, and copper plating treatment having a copper thickness of 25 µm was performed. Subsequently, an annealing treatment was performed at 190 ° C. for 60 minutes in a hot air circulation drying furnace to obtain a test substrate subjected to copper plating treatment. The test board | substrate was cut out to 1 cm in width and 7 cm or more in length, and the peeling strength in 90 degree | times was calculated | required using the 90 degree print peeling jig using the compact bench testing machine EZ-SX made from Shimadzu Corporation. (Circle) and 2.5N / m or more and less than 4.5N / m, (triangle | delta) and a thing less than 2.5N / m were made into those whose evaluation is 4.5N / m or more. The results are shown in Tables 13 to 15. Moreover, if peeling strength is 4.5N / m or more, it is thought that there is no problem of peeling also in a high precision circuit. This criterion is a very strict evaluation condition.

(Photocurable thermosetting composition)

Each composition shown in Tables 16-21 was apply | coated to the PET film with a thickness of 38 micrometers with the applicator of a gap of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Thereafter, the resin layer of each composition was laminated by pressing a FR-4 copper clad laminate (copper thickness 18 µm) having a size of 150 mm x 100 mm (copper thickness of 18 µm) for 60 seconds with a vacuum laminator under a condition of 60 ° C and a pressure of 0.5 MPa, using the printed circuit board a metal halide lamp exposure machine 700mJ / cm ² the entire surface exposed after the peeling off the PET _{film, 30 ℃ 1wt% Na 2 CO} 3 as the developer for a was developed for 60 seconds in the developing cartridge. Then, it hardened | cured by heating 150 degreeC 60 minutes in a hot air circulation type drying furnace. Subsequently, permanganic acid desmear (manufactured by ATOTECH), electroless copper plating (through cup PEA, manufactured by Uemura Kogyo Co., Ltd.), and electrolytic copper plating were processed in order, and copper plating having a copper thickness of 25 µm was performed. Subsequently, an annealing treatment was performed at 190 ° C. for 60 minutes in a hot air circulation drying furnace to obtain a test substrate subjected to copper plating treatment. The test board | substrate was cut out to 1 cm in width and 7 cm or more in length, and the peeling strength in 90 degree | times was calculated | required using the 90 degree print peeling jig using the compact bench testing machine EZ-SX made from Shimadzu Corporation. Evaluation made (circle) and the thing of 2.5N / m or more and less than 4.5N / m (triangle | delta) and the thing less than 2.5N / m what was 4.5N / m or more as x. The results are shown in Tables 16 to 21.

[Solder heat resistance]

(Thermosetting composition)

Each composition shown in Tables 13 to 15 was formed on a 150 mm × 95 mm, 1.6 mm thick FR-4 copper clad laminate by 80 mesh Tetron bias plate screen printing to form a whole surface solid pattern, and 80 ° C. 30 in a hot air circulating drying furnace. It dried for 1 minute, and then heat-cured at 180 degreeC for 30 minutes, and obtained the test piece. The rosin type flux was apply | coated to the hardened | cured material side of the composition of this test piece, it flowed into the 260 degreeC solder layer for 60 second, and it wash | cleaned with propylene glycol monomethyl ether acetate, and then it wash | cleaned with ethanol. About the test piece, swelling and peeling of the coating film, and the change of the surface state were observed visually. The thing which showed abnormality by swelling and peeling, surface melt | dissolution, softening, etc. in a coating film was evaluated as (circle) and what was not seen. The evaluation results are shown in Tables 13 to 15.

(Photocurable thermosetting composition)

Each composition shown in Tables 16-21 was formed in 80 mesh Tetron bias plate screen printing on FR-4 copper clad laminated board of size 150mm * 95mm, 1.6mm thick, and 80 degreeC 30 in hot-air circulation type drying furnace. to minutes. Thereafter, using a printed circuit board a metal halide lamp exposure machine 700mJ of the entire surface exposure, _{and, 30 ℃ 1wt% Na 2 CO} 3 to / cm ² for a developing solution, and then developed for 60 seconds in the developing cartridge. Then, it heat-hardened 150 degreeC 60 minutes in the hot-air circulation type drying furnace, and obtained the test piece. The rosin type flux was apply | coated to the hardened | cured material side of the composition of this test piece, it flowed into the 260 degreeC solder layer for 60 second, and it wash | cleaned with propylene glycol monomethyl ether acetate, and then it wash | cleaned with ethanol. The test piece was visually observed to observe the swelling and peeling of the coating film and the change of the surface state. The thing which showed abnormality by swelling and peeling, surface melt | dissolution, softening, etc. in a coating film was evaluated as (circle) and what was not seen. The evaluation results are shown in Tables 16 to 21.

[Insulation]

(Thermosetting composition)

Each composition shown in Tables 13-15 was apply | coated to the PET film of thickness 38micrometer with the applicator of gap 120micrometer, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Subsequently, each composition was pressed for 60 seconds under a condition of 60 ° C. and a pressure of 0.5 MPa using a vacuum laminator on an A coupon of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm thick FR-4 substrate with a thickness of 35 μm copper. The resin layer was laminated, the PET film was peeled off, and heated at 180 ° C. for 30 minutes in a hot air circulation drying furnace to cure. Subsequently, the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 was cut to form an electrically independent terminal (cut at the dotted line in Fig. 3-2). Then, a bias of 500 V DC was applied so that the upper portion of the A coupon was the cathode and the lower portion was the anode, and the insulation resistance value was measured. Evaluation made (circle) that an insulation resistance value is 100 G (ohm) or more, and made the thing whose insulation resistance value is less than 100 G (ohm). The results are shown in Tables 13 to 15.

(Photocurable thermosetting composition)

Each composition shown in Tables 16-21 was apply | coated to the PET film with a thickness of 38 micrometers with the applicator of a gap of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Subsequently, each composition was pressed for 60 seconds under a condition of 60 ° C. and a pressure of 0.5 MPa using a vacuum laminator on an A coupon of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm thick FR-4 substrate with a thickness of 35 μm copper. The resin layer was laminated, and the entire surface was exposed to 700 mJ / cm ² using a metal halide lamp exposure machine for a printed wiring board, and then the PET film was peeled off, using a developer solution of 1 wt% Na ₂ CO ₃ at 30 ° C. for 60 seconds using a developer. Developed. Then, it hardened | cured by heating 150 degreeC 60 minutes in a hot air circulation type drying furnace. Subsequently, the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 was cut to form an electrically independent terminal. Then, a bias of DC 500V was applied so that the upper portion of the A coupon was the negative electrode and the lower portion was the positive electrode, and the insulation resistance value was measured. Evaluation made (circle) that an insulation resistance value is 100 G (ohm) or more, and made the thing whose insulation resistance value is less than 100 G (ohm). The results are shown in Tables 16 to 21.

[Relative dielectric constant, dielectric loss tangent]

(Thermosetting composition)

Each composition shown in Tables 13-15 was apply | coated to the PET film with a thickness of 38 micrometers with the applicator of 200 micrometers, and it dried at 90 degreeC for 20 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Thereafter, the electrolytic copper foil having a thickness of 18 µm was pressed against the substrate fixed with a gloss surface on a FR-4 copper clad laminate having a thickness of 1.6 mm with a vacuum laminator for 60 seconds under a vacuum laminator at a pressure of 0.5 MPa for 60 seconds. The resin layer was laminated, the PET film was peeled off, and heated at 180 ° C. for 30 minutes in a hot air circulation drying furnace to cure. And the fixed tape was peeled off, the electrolytic copper foil was peeled off, it cut out to the magnitude | size of 1.7 mm x 100 mm, and it was set as the sample for evaluation. The measurement was performed with the network analyzer E-507 by a Keysight Technologies company using the cavity resonator (5GHz) by Kanto Den-shi Ohyo Kaihats Corporation. In the evaluation of the dielectric constant, the average value measured three times was less than 2.8, and those having 2.8 or more and less than 3.0 were Δ and 3.0 or more. Evaluation of the dielectric loss tangent was made into (circle) and thing of 0.02 or more that the average value measured three times was less than 0.02. Each result is shown to Tables 13-15.

(Photocurable thermosetting composition)

Each composition shown in Tables 16-21 was apply | coated to the PET film of thickness 38micrometer with the applicator of 200 micrometers, and it dried at 80 degreeC for 30 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Thereafter, the electrolytic copper foil having a thickness of 18 µm was pressed against the substrate fixed with a gloss surface on a FR-4 copper clad laminate having a thickness of 1.6 mm with a vacuum laminator for 60 seconds under a vacuum laminator at a pressure of 0.5 MPa for 60 seconds. the number of the laminated resin layer and using an aperture mask of 1.7mm × 100mm, the printed wiring board in a metal halide lamp for exposure device after the exposure to 700mJ / cm ² 1wt% of peeling off the PET film, and 30 ℃ Na ₂ CO ₃ Using the developing solution, it developed for 60 second with the developing machine. Then, it hardened | cured by heating 150 degreeC 60 minutes in a hot air circulation type drying furnace. And the fixed tape was peeled off, the electrolytic copper foil was peeled off, and it was set as the sample for evaluation. The measurement was performed with the network analyzer E-507 by a Keysight Technologies company using the cavity resonator (5GHz) by Kanto Den-shi Ohyo Kaihats Corporation. In the evaluation of the dielectric constant, the average value measured three times was less than 3.0, and the one having a value of 3.0 or more and less than 3.2 was Δ and the thing of 3.2 or more. Evaluation of the dielectric loss tangent was made into (circle) and thing of 0.02 or more that the average value measured three times was less than 0.02. Each result is shown in Tables 16-21.

* 3-1) Thermosetting resin 3-1: Cyclohexanone varnish (cyclic ether compound which has a dicyclopentadiene skeleton) of 50 mass% of epiclonal HP-7200 solid content

* 3-2) Thermosetting resin 3-2: Cyclohexanone varnish (cyclic ether compound which has a dicyclopentadiene skeleton) of 50 mass% of Tactix 756 solid content

* 3-3) Thermosetting resin 3-3: cyclohexanone varnish of 50 mass% of solid content made by Epiclone N-740 DIC Co., Ltd.

* 3-4) Thermosetting resin 3-4: Epiclon 830 DIC Corporation

* 3-5) Thermosetting resin 3-5: manufactured by JER827 Mitsubishi Chemical Corporation

* 3-6) Thermosetting resin 3-6: Resistant GDP-6085 solid content 60 mass% cyclohexanone varnish (phenol resin having a dicyclopentadiene skeleton)

* 3-7) Thermosetting resin 3-7: 60 mass% cyclohexanone varnish by HF-1 Meiwa Kasei Co., Ltd. solid content

* 3-8) Curing catalyst 3-1: 2E4MZ (2-ethyl-4-methylimidazole) Shikoku Kasei Kogyo Co., Ltd. make

* 3-9) Filler 3-1: Admafine SO-C2 Co., Ltd.

* 3-10) Organic Solvent 3-1: Dimethylformamide

* 3-11) Antifoaming agent 3-1: BYK-352 BIC Chemy Japan Co., Ltd.

* 3-18) Filler 3-2: B-30 barium sulfate manufactured by Sakai Kagaku Kogyo Co., Ltd.

* 3-19) Filler 3-3: DAW-07 Alumina manufactured by Denka Corporation

* 3-20) Dispersant 3-1: manufactured by DISPERBYK-111 Big Chemistry

* 3-12) Curing catalyst 3-2: Pulverized melamine Nissan Chemical Industries, Ltd.

* 3-13) Curing Catalyst 3-3: Dicyandiamide

* 3-14) Photopolymerization Initiator 3-1: Irgacure 907 manufactured by BASF Corporation

* 3-15) Photocurable resin 3-1: dipentaerythritol tetraacrylate

* 3-16) Thermosetting resin 3-8: TEPIC-H (triglycidyl isocyanurate) manufactured by Nissan Chemical Industries, Ltd.

* 3-17) Colorant 3-1: Phthalocyanine Blue

As apparent from the results shown in Tables 13 to 21, at least one selected from the group consisting of fine powder such as fine cellulose fibers, a cyclic ether compound having a dicyclopentadiene skeleton, and a phenol resin having a dicyclopentadiene skeleton By including 1 type, it was confirmed that the curable resin composition which is excellent in insulation reliability, has low dielectric properties, and has favorable adhesiveness of hardened | cured material and plated copper is obtained. Moreover, it was confirmed from the evaluation result of solder heat resistance that each composition of the Example was excellent in heat resistance and chemical-resistance, and can be used as a composition for wiring boards.

Fourth Example

As the fine cellulose fibers CNF1 to CNF3 and the cellulose nanocrystal particles CNC1 and CNC2, the same production examples 1 to 5 as those of the first embodiment were used, and as varnishes 1 to varnish 3, the synthesis example 1 similar to the second embodiment was used. 3 to 3 were used.

According to the description of the following Tables 22-30, after mixing and stirring each component, it was made to disperse | distribute 6 times repeatedly using the high-pressure homogenizer Nanovater NVL-ES008 of Yoshida Kikai Kogyo Co., Ltd., and each composition was manufactured. In addition, the numerical value in Tables 22-30 shows a mass part.

[Solder heat resistance]

(Thermosetting composition)

Each composition shown in Tables 22 to 25 was formed on an FR-4 copper clad laminate having a size of 150 mm x 95 mm and 1.6 mm thick by 80 mesh Tetron bias plate screen printing to form a whole surface solid pattern, and 80 ° C 30 in a hot air circulating drying furnace. It dried for 1 minute, and then heat-cured at 180 degreeC for 30 minutes, and obtained the test piece. The rosin type flux was apply | coated to the hardened | cured material side of the composition of this test piece, it flowed into the 260 degreeC solder layer for 60 second, and it wash | cleaned with propylene glycol monomethyl ether acetate, and then it wash | cleaned with ethanol. About the test piece, swelling and peeling of the coating film, and the change of the surface state were observed visually. The thing which showed abnormality by swelling and peeling, surface melt | dissolution, softening, etc. in a coating film was evaluated as (circle) and what was not seen. The evaluation results are shown in Tables 22 to 25.

(Photocurable thermosetting composition)

Each composition shown in Tables 26 to 30 was formed on an FR-4 copper clad laminate having a size of 150 mm x 95 mm and 1.6 mm thick by 80 mesh Tetron bias plate screen printing to form a whole surface solid pattern, and 80 ° C 30 in a hot air circulating drying furnace. to minutes. Thereafter, using a printed circuit board a metal halide lamp exposure machine 700mJ of the entire surface exposure, _{and, 30 ℃ 1wt% Na 2 CO} 3 to / cm ² for a developing solution, and then developed for 60 seconds in the developing cartridge. Then, it heat-hardened 150 degreeC 60 minutes in the hot-air circulation type drying furnace, and obtained the test piece. The rosin type flux was apply | coated to the hardened | cured material side of the composition of this test piece, it flowed into the 260 degreeC solder layer for 60 second, and it wash | cleaned with propylene glycol monomethyl ether acetate, and then it wash | cleaned with ethanol. The test piece was visually observed to observe the swelling and peeling of the coating film and the change of the surface state. The thing which showed abnormality by swelling and peeling, surface melt | dissolution, softening, etc. in a coating film was evaluated as (circle) and what was not seen. The evaluation results are shown in Tables 26 to 30.

[Insulation]

(Thermosetting composition)

Each composition shown in Tables 22-25 was apply | coated to the PET film of thickness 38micrometer with the applicator of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Subsequently, each composition was pressed for 60 seconds under a condition of 60 ° C. and a pressure of 0.5 MPa using a vacuum laminator on an A coupon of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm thick FR-4 substrate with a thickness of 35 μm copper. The resin layer was laminated, the PET film was peeled off, and heated at 180 ° C. for 30 minutes in a hot air circulation drying furnace to cure. Subsequently, the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 was cut to form an electrically independent terminal (cut at the dotted line in Fig. 4-2). Then, a bias of 500 V DC was applied so that the upper portion of the A coupon was the cathode and the lower portion was the anode, and the insulation resistance value was measured. Evaluation made (circle) that an insulation resistance value is 100 G (ohm) or more, and made the thing whose insulation resistance value is less than 100 G (ohm). The results are shown in Tables 22 to 25.

(Photocurable thermosetting composition)

Each composition shown in Tables 26-30 was apply | coated to the PET film of thickness 38micrometer with the applicator of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Subsequently, each composition was pressed for 60 seconds under a condition of 60 ° C. and a pressure of 0.5 MPa using a vacuum laminator on an A coupon of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm thick FR-4 substrate with a thickness of 35 μm copper. The resin layer was laminated, and the entire surface was exposed to 700 mJ / cm ² using a metal halide lamp exposure machine for a printed wiring board, and then the PET film was peeled off, using a developer solution of 1 wt% Na ₂ CO ₃ at 30 ° C. for 60 seconds using a developer. Developed. Then, it hardened | cured by heating 150 degreeC 60 minutes in a hot air circulation type drying furnace. Subsequently, the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 was cut to form an electrically independent terminal. Then, a bias of DC 500V was applied so that the upper portion of the A coupon was the negative electrode and the lower portion was the positive electrode, and the insulation resistance value was measured. Evaluation made (circle) that an insulation resistance value is 100 G (ohm) or more, and made the thing whose insulation resistance value is less than 100 G (ohm). The results are shown in Tables 26 to 30.

[Removability of Smear]

(Thermosetting Resin Composition)

Each composition shown in Tables 22-25 was apply | coated to the PET film of thickness 38micrometer with the applicator of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Thereafter, the resin layer of each composition was laminated on the FR-4 copper clad laminate (copper thickness 18 μm) having a size of 150 mm × 100 mm and pressed for 60 seconds under a condition of 60 ° C. and a pressure of 0.5 MPa using a vacuum laminator, The PET film was peeled off, and it heated and hardened | cured by 180 degreeC 30 minutes in a hot air circulation type drying furnace, and obtained the test piece.

The test piece was made a hole with a beam diameter of 100 micrometers with the carbon dioxide laser drilling machine LC-2K212 (made by Hitachi Via Mechanics Co., Ltd.). Next, permanganic acid desmear (made by ATOTECH) was performed. Desmear's standard process is the swelling process (60 ° C 5 minutes), permanganic acid etching process (80 ° C 20 minutes) and neutralization process (40 ° C 5 minutes), but in the permanganic acid etching step, 10 minutes, 15 minutes, 20 minutes The test was conducted in three steps of minutes.

And the punching part was observed at 3500 times magnification with the scanning electron microscope JSM-6610LV (made by Nippon Denshi Corporation), and the presence or absence of the smear on the copper surface was confirmed. The evaluation made x that the smear disappeared by 10-minute permanganic acid etching, and that smear disappeared in 15 minutes, (triangle | delta), and that smear disappeared barely in 20 minutes. The results are shown in Tables 22 to 25.

(Photocurable thermosetting resin composition)

Each composition shown in Tables 26-30 was apply | coated to the PET film of thickness 38micrometer with the applicator of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Thereafter, the resin layer of each composition was laminated by pressing a FR-4 copper clad laminate (copper thickness 18 µm) having a size of 150 mm x 100 mm (copper thickness of 18 µm) for 60 seconds with a vacuum laminator under a condition of 60 ° C and a pressure of 0.5 MPa, using the printed circuit board a metal halide lamp exposure machine 700mJ / cm ² the entire surface exposed after the peeling off the PET _{film, 30 ℃ 1wt% Na 2 CO} 3 as the developer for a was developed for 60 seconds in the developing cartridge. Then, it hardened | cured by heating 150 degreeC 60 minutes in a hot air circulation type drying furnace. It hardened and the test piece was obtained.

The test piece was made a hole with a beam diameter of 100 micrometers with the carbon dioxide laser drilling machine LC-2K212 (made by Hitachi Via Mechanics Co., Ltd.). Next, using permanganic acid desmear (manufactured by ATOTECH), in the permanganic acid etching step, the test was conducted in three steps of 10 minutes, 15 minutes, and 20 minutes.

And the punching part was observed at 3500 times magnification with the scanning electron microscope JSM-6610LV (made by Nippon Denshi Corporation), and the presence or absence of the smear on the copper surface was confirmed. The evaluation made x that the smear disappeared by 10-minute permanganic acid etching, and that smear disappeared in 15 minutes, (triangle | delta), and that smear disappeared barely in 20 minutes. The results are shown in Tables 26 to 30.

[Measurement of Peel Strength and Ra]

(Thermosetting Resin Composition)

Each composition shown in Tables 22-25 was apply | coated to the PET film of thickness 38micrometer with the applicator of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Subsequently, the resin layer of each composition was laminated by pressing the FR-4 copper clad laminate (copper thickness 18 µm) having a size of 150 mm x 100 mm for 60 seconds with a vacuum laminator under a condition of 60 ° C and a pressure of 0.5 MPa, The PET film was peeled off and cured by heating 180 ° C. for 30 minutes in a hot air circulation drying furnace. Subsequently, using a permanganic acid desmear (manufactured by ATOTECH Co., Ltd.), a sample of two stages was produced in 10 minutes for the Example, 10 minutes, and 20 minutes for the Comparative Example. As a roughness measurement of the surface of a sample, Ra (arithmetic mean roughness) was measured using the optical interference microscope Contour GT (made by BRUKER). Ra represents an arithmetic mean roughness, is a value obtained by drawing a line at the center of the cross-sectional curve, dividing the total area on the curve obtained by the center line by the length, the larger the value, the greater the roughness, and the smaller the value, the higher the smoothness. Ra is defined in JIS B0031: 2003. The results are shown in Tables 22 to 25.

Subsequently, the test piece which finished until the desmear was processed in order of electroless copper plating (through cup PEA, Uemura Co., Ltd.), electrolytic copper plating process, and copper plating process of 25 micrometers of copper thicknesses was performed. Subsequently, an annealing treatment was performed at 190 ° C. for 60 minutes in a hot air circulation drying furnace to obtain a test substrate subjected to copper plating treatment. The test board | substrate was cut out to 1 cm in width and 7 cm or more in length, and the peeling strength in 90 degree | times was calculated | required using the 90 degree print peeling jig using the compact bench testing machine EZ-SX made from Shimadzu Corporation. (Circle) and 2.5N / m or more and less than 4.5N / m, (triangle | delta) and a thing less than 2.5N / m were made into those whose evaluation is 4.5N / m or more. The results are shown in Tables 22 to 25.

(Photocurable thermosetting resin composition)

Each composition shown in Tables 26-30 was apply | coated to the PET film of thickness 38micrometer with the applicator of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Thereafter, the resin layer of each composition was laminated by pressing a FR-4 copper clad laminate (copper thickness 18 µm) having a size of 150 mm x 100 mm (copper thickness of 18 µm) for 60 seconds with a vacuum laminator under a condition of 60 ° C and a pressure of 0.5 MPa, using the printed circuit board a metal halide lamp exposure machine 700mJ / cm ² the entire surface exposed after the peeling off the PET _{film, 30 ℃ 1wt% Na 2 CO} 3 as the developer for a was developed for 60 seconds in the developing cartridge. Then, it hardened | cured by heating 150 degreeC 60 minutes in a hot air circulation type drying furnace. Subsequently, using a permanganic acid desmear (manufactured by ATOTECH Co., Ltd.), a sample of two stages was produced in 10 minutes for the Example, 10 minutes, and 20 minutes for the Comparative Example. Ra was measured using the optical interference microscope Contour GT (made by BRUKER) as a roughness measurement of the surface of a sample. The results are shown in Tables 26 to 30.

Subsequently, the test piece which finished until the desmear was processed in order of electroless copper plating (through cup PEA, Uemura Co., Ltd.), electrolytic copper plating process, and copper plating process of 25 micrometers of copper thicknesses was performed. Subsequently, an annealing treatment was performed at 190 ° C. for 60 minutes in a hot air circulation drying furnace to obtain a test substrate subjected to copper plating treatment. The test board | substrate was cut out to 1 cm in width and 7 cm or more in length, and the peeling strength in 90 degree | times was calculated | required using the 90 degree print peeling jig using the compact bench testing machine EZ-SX made from Shimadzu Corporation. (Circle) and 2.5N / m or more and less than 4.5N / m, (triangle | delta) and a thing less than 2.5N / m were made into those whose evaluation is 4.5N / m or more. The results are shown in Tables 26 to 30.

* 4-1) Phenoxy resin 4-1: Cyclohexanone varnish of 30 mass% of solid content by YX6954 Mitsubishi Chemical Corporation

* 4-2) Phenoxy resin 4-2: 1,256 cyclohexanone varnish of 30 mass% of solids made by Mitsubishi Chemical Corporation

* 4-3) Phenoxy resin 4-3: Cyclohexanone varnish of 4250 Mitsubishi Kagaku Co., Ltd. solid content 30 mass%

* 4-4) Thermosetting resin 4-1: Cyclohexanone varnish of 50 mass% of solid content made by Epiclone N-740 DIC Co., Ltd.

* 4-5) Thermosetting resin 4-2: Epiclon 830 DIC Corporation

* 4-6) Thermosetting resin 4-3: made by JER827 Mitsubishi Chemical Corporation

* 4-7) Thermosetting resin 4-4: 60 mass% cyclohexanone varnish by HF-1 Maya and Kasei Co., Ltd. solid content

* 4-8) Curing catalyst 4-1: 2E4MZ (2-ethyl-4-methylimidazole) Shikoku Kasei Kogyo Co., Ltd. make

* 4-9) Filler 4-1: Admafine SO-C2 Admatex Co., Ltd. (Silica)

* 4-10) Organic Solvent 4-1: Dimethylformamide

* 4-11) Antifoam 4-1: BYK-352 BIC Chemy Japan Co., Ltd.

* 4-18) Filler 4-2: B-30 Sakai Kagaku Kogyo Co., Ltd.

* 4-19) Filler 4-3: Alumina made by DAW-07 Denka Co., Ltd.

* 4-20) Dispersant 4-1: manufactured by DISPERBYK-111 Big Chemistry

* 4-12) Curing catalyst 4-2: Pulverized melamine Nissan Chemical Industries, Ltd.

* 4-13) Curing Catalyst 4-3: Dicyandiamide

* 4-14) Photopolymerization Initiator 4-1: Irgacure 907 manufactured by BASF Corporation

* 4-15) Photocurable resin 4-1: dipentaerythritol tetraacrylate

* 4-16) Thermosetting resin 4-5: TEPIC-H (triglycidyl isocyanurate) manufactured by Nissan Chemical Industries, Ltd.

* 4-17) Colorant 4-1: Phthalocyanine Blue

As apparent from the results shown in Tables 22 to 30, by containing fine powder such as fine cellulose fibers and phenoxy resin, smear removal by laser processing in the desmear process is possible and high frequency transmission is achieved. It was confirmed that curable resin composition which is excellent also in peeling strength is obtained, having small surface roughness which is favorable for it. Moreover, it was confirmed from the evaluation result of solder heat resistance that each composition of the Example was excellent in heat resistance and chemical-resistance, and can be used as a composition for wiring boards.

Fifth Embodiment

As the fine cellulose fibers CNF1 to CNF3 and the cellulose nanocrystal particles CNC1 and CNC2, the same production examples 1 to 5 as those of the first embodiment were used, and as varnishes 1 to varnish 3, the synthesis example 1 similar to the second embodiment was used. 3 to 3 were used.

According to the description of the following Table 31-39, after mixing and stirring each component, it was made to disperse | distribute it 6 times using the high-pressure homogenizer Nanovater NVL-ES008 of Yoshida Kikai Kogyo Co., Ltd., and each composition was manufactured. In addition, the numerical value of Tables 31-39 shows a mass part.

[Expansion of plated copper]

(Thermosetting composition)

Each composition shown in Tables 31-33 was apply | coated to the PET film of thickness 38micrometer with the applicator of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Subsequently, the resin layer of each composition was laminated by pressing the FR-4 copper clad laminate (copper thickness 18 µm) having a size of 150 mm x 100 mm for 60 seconds with a vacuum laminator under a condition of 60 ° C and a pressure of 0.5 MPa, The PET film was peeled off and cured by heating 180 ° C. for 30 minutes in a hot air circulation drying furnace. Subsequently, permanganic acid desmear (manufactured by ATOTECH Co., Ltd.), electroless copper plating (through cup PEA, manufactured by Uemura Kogyo Co., Ltd.), and electrolytic copper plating treatment were performed in this order, and copper plating treatment having a copper thickness of 25 µm was performed. Subsequently, an annealing treatment was performed at 190 ° C. for 60 minutes in a hot air circulation drying furnace to obtain a test substrate subjected to copper plating treatment. And after passing through the reflow furnace of the peak temperature of 265 degreeC three times, the expansion of plating copper was visually evaluated. (Circle) which did not fully expand among 10 test board | substrates, (circle) which showed expansion within 1 sheet of 10 test substrates, (triangle | delta) and what showed expansion to 2 or more sheets of 10 test substrates were made into x. The results are shown in Tables 31 to 33.

(Photocurable thermosetting composition)

Each composition shown in Tables 34-39 was apply | coated to the PET film of thickness 38micrometer by the applicator of gap 120micrometer, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Thereafter, the resin layer of each composition was laminated by pressing a FR-4 copper clad laminate (copper thickness 18 µm) having a size of 150 mm x 100 mm (copper thickness of 18 µm) for 60 seconds with a vacuum laminator under a condition of 60 ° C and a pressure of 0.5 MPa, using the printed circuit board a metal halide lamp exposure machine 700mJ / cm ² the entire surface exposed after the peeling off the PET _{film, 30 ℃ 1wt% Na 2 CO} 3 as the developer for a was developed for 60 seconds in the developing cartridge. Then, it hardened | cured by heating 150 degreeC 60 minutes in a hot air circulation type drying furnace. Subsequently, permanganic acid desmear (manufactured by ATOTECH), electroless copper plating (through cup PEA, manufactured by Uemura Kogyo Co., Ltd.), and electrolytic copper plating were processed in order, and copper plating having a copper thickness of 25 µm was performed. Subsequently, an annealing treatment was performed at 190 ° C. for 60 minutes in a hot air circulation drying furnace to obtain a test substrate subjected to copper plating treatment. And after passing through the reflow furnace of the peak temperature of 265 degreeC three times, the expansion of plating copper was visually evaluated. (Circle) which did not fully expand among 10 test board | substrates, (circle) which showed expansion within 1 sheet of 10 test substrates, (triangle | delta) and what showed expansion to 2 or more sheets of 10 test substrates were made into x. The results are shown in Tables 34 to 39.

[Solder heat resistance]

(Thermosetting composition)

Each composition shown in Tables 31 to 33 was formed on an 80 mesh Tetron bias plate screen printing on FR-4 copper clad laminates having a size of 150 mm x 95 mm and 1.6 mm thick, and 80 ° C 30 in a hot air circulation drying furnace. It dried for 1 minute, and then heat-cured at 180 degreeC for 30 minutes, and obtained the test piece. The rosin type flux was apply | coated to the hardened | cured material side of the composition of this test piece, it flowed into the 260 degreeC solder layer for 60 second, and it wash | cleaned with propylene glycol monomethyl ether acetate, and then it wash | cleaned with ethanol. About the test piece, swelling and peeling of the coating film, and the change of the surface state were observed visually. The thing which showed abnormality by swelling and peeling, surface melt | dissolution, softening, etc. in a coating film was evaluated as (circle) and what was not seen. The evaluation results are shown in Tables 31 to 33.

(Photocurable thermosetting composition)

Each composition shown in Tables 34 to 39 was formed on an 80 mesh Tetron bias plate screen printing on a FR-4 copper clad laminate having a size of 150 mm x 95 mm and 1.6 mm thick, and 80 ° C 30 in a hot air circulating drying furnace. to minutes. Thereafter, using a printed circuit board a metal halide lamp exposure machine 700mJ of the entire surface exposure, _{and, 30 ℃ 1wt% Na 2 CO} 3 to / cm ² for a developing solution, and then developed for 60 seconds in the developing cartridge. Then, it heat-hardened 150 degreeC 60 minutes in the hot-air circulation type drying furnace, and obtained the test piece. The rosin type flux was apply | coated to the hardened | cured material side of the composition of this test piece, it flowed into the 260 degreeC solder layer for 60 second, and it wash | cleaned with propylene glycol monomethyl ether acetate, and then it wash | cleaned with ethanol. The test piece was visually observed to observe the swelling and peeling of the coating film and the change of the surface state. The thing which showed abnormality by swelling and peeling, surface melt | dissolution, softening, etc. in a coating film was evaluated as (circle) and what was not seen. The evaluation results are shown in Tables 34 to 39.

[Insulation]

(Thermosetting composition)

Each composition shown in Tables 31-33 was apply | coated to the PET film of thickness 38micrometer with the applicator of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Subsequently, each composition was pressed for 60 seconds under a condition of 60 ° C. and a pressure of 0.5 MPa using a vacuum laminator on an A coupon of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm thick FR-4 substrate with a thickness of 35 μm copper. The resin layer was laminated, the PET film was peeled off, and heated at 180 ° C. for 30 minutes in a hot air circulation drying furnace to cure. Subsequently, the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 was cut to form an electrically independent terminal (cut at the dotted line in Fig. 5-2). Then, a bias of DC 500V was applied so that the upper portion of the A coupon was the negative electrode and the lower portion was the positive electrode, and the insulation resistance value was measured. Evaluation made (circle) that an insulation resistance value is 100 G (ohm) or more, and made the thing whose insulation resistance value is less than 100 G (ohm). The results are shown in Tables 31 to 33.

(Photocurable thermosetting composition)

Each composition shown in Tables 34-39 was apply | coated to the PET film of thickness 38micrometer by the applicator of gap 120micrometer, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Subsequently, each composition was pressed for 60 seconds under a condition of 60 ° C. and a pressure of 0.5 MPa using a vacuum laminator on an A coupon of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm thick FR-4 substrate with a thickness of 35 μm copper. The resin layer was laminated, and the entire surface was exposed to 700 mJ / cm ² using a metal halide lamp exposure machine for a printed wiring board, and then the PET film was peeled off, using a developer solution of 1 wt% Na ₂ CO ₃ at 30 ° C. for 60 seconds using a developer. Developed. Then, it hardened | cured by heating 150 degreeC 60 minutes in a hot air circulation type drying furnace. Subsequently, the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 was cut to form an electrically independent terminal. Then, a bias of DC 500V was applied so that the upper portion of the A coupon was the negative electrode and the lower portion was the positive electrode, and the insulation resistance value was measured. Evaluation made (circle) that an insulation resistance value is 100 G (ohm) or more, and made the thing whose insulation resistance value is less than 100 G (ohm). The results are shown in Tables 34 to 39.

[Production of Sample for Thermal Expansion Measurement]

(Thermosetting Resin Composition)

Each composition shown in Tables 31-33 was apply | coated to the PET film of thickness 38micrometer with the applicator of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Then, it crimped | bonded for 60 second on 60 degreeC and the pressure of 0.5 MPa on the copper foil of thickness 18micrometer with a vacuum laminator, laminated the resin layer of each composition, and peeled off the PET film. Next, it heated and hardened | cured by 180 degreeC 30 minutes in a hot-air circulation type drying furnace, peeled copper foil, and obtained the sample of the cured film.

(Photocurable thermosetting resin composition)

A copper foil having a thickness of 18 μm was applied to a FR-4 copper clad laminate having a thickness of 1.6 mm, and each composition shown in Tables 34 to 39 was applied with an applicator having a gap of 120 μm, and dried at 90 ° C. for 10 minutes in a hot air circulation drying furnace. Then, the negative mask with a pattern of 3 mm width x 30 mm length was stuck, and it exposed at 700 mJ / cm <^2> with the metal halide lamp exposure machine for printed wiring boards. Then, using a 30 ℃ 1wt% Na ₂ CO ₃ in a developing solution, and then developed for 60 seconds in the developing cartridge. Then, it heated and hardened | cured by 150 degreeC 60 minutes in a hot air circulation type drying furnace, peeled copper foil, and obtained the sample of the cured film.

[Measurement of thermal expansion rate]

(Thermosetting Resin Composition)

The produced thermal expansion sample was cut into 3 mm width x 30 mm length. The test piece was heated to 5 ° C./min to 20 to 250 ° C. in a tension mode using a TMA (Thermomechanical Analysis) T400 manufactured by T-A Instruments Co., Ltd. It measured by reducing by 5 degree-C / min to 20 degreeC. The average thermal expansion coefficient (alpha) 1 of 30 degreeC-100 degreeC at the time of temperature fall, and the average thermal expansion coefficient (alpha) 2 of 200 degreeC-230 degreeC were calculated | required. Moreover, evaluation was performed from the value. (circle) and less than 35 ppm of (alpha) 1 were made into (triangle | delta) and the thing of 35 ppm or more as what is less than 25 ppm. (circle) and less than 95 ppm of (alpha) 2 were made into (triangle | delta) and the thing of 95 ppm or more as thing less than 75 ppm. The results are shown in Tables 31 to 33.

(Photocurable thermosetting resin composition)

Except having used the produced sample as it was, it carried out by the method similar to a thermosetting resin composition. The results are shown in Tables 34 to 39.

* 5-1) Thermosetting resin 5-1: Cyclohexanone varnish (cyclic ether compound which has a biphenyl skeleton) of 50 mass% of solid content by NC-3000H Nippon Kayaku Co., Ltd.

* 5-2) Thermosetting resin 5-2: Cyclohexanone varnish (cyclic ether compound which has a biphenyl skeleton) of 50 mass% of solid content by YX-4000 Mitsubishi Chemical Corporation

* 5-3) Thermosetting resin 5-3: Cyclohexanone varnish of 50 mass% of solid content made by Epiclone N-740 DIC Co., Ltd.

* 5-4) Thermosetting resin 5-4: Epiclon 830 DIC Corporation

* 5-5) Thermosetting resin 5-5: made by JER827 Mitsubishi Chemical Corporation

* 5-6) Thermosetting resin 5-6: GPH-103 Nippon Kayaku Co., Ltd. solid content 60 mass% cyclohexanone varnish (phenol resin which has a biphenyl skeleton)

* 5-7) Thermosetting resin 5-7: 60 mass% cyclohexanone varnish by HF-1 Meiwa Kasei Co., Ltd. solid content

* 5-8) Curing catalyst 5-1: 2E4MZ (2-ethyl-4-methylimidazole) Shikoku Kasei Kogyo Co., Ltd. make

* 5-9) Filler 5-1: Admafine SO-C2 Admatex Co., Ltd. (Silica)

* 5-10) Organic Solvent 5-1: Dimethylformamide

* 5-11) Antifoam 5-1: BYK-352 BIC Chemy Japan Co., Ltd.

* 5-18) Thermosetting resin 5-8: Bisphenol A diacetate Tokyo Kasei Kogyo Co., Ltd. (active ester compound)

* 5-19) Filler 5-2: B-30 Sakai Kagaku Kogyo Co., Ltd.

* 5-20) Filler 5-3: Alumina made by DAW-07 Denka Co., Ltd.

* 5-21) Dispersant 5-1: manufactured by DISPERBYK-111 Big Chemistry

* 5-12) Curing catalyst 5-2: Product made by pulverized melamine Nissan Kagaku Co., Ltd.

* 5-13) Curing Catalyst 5-3: Dicyandiamide

* 5-14) Photopolymerization Initiator 5-1: Irgacure 907 manufactured by BASF Corporation

* 5-15) Photocurable resin 5-1: dipentaerythritol tetraacrylate

* 5-16) Thermosetting resin 5-9: TEPIC-H (triglycidyl isocyanurate) manufactured by Nissan Chemical Industries, Ltd.

* 5-17) Colorant 5-1: Phthalocyanine Blue

As apparent from the results shown in Tables 31 to 39, it contains at least one selected from the group consisting of fine powders such as fine cellulose fibers, a cyclic ether compound having a biphenyl skeleton and a phenol resin having a biphenyl skeleton. By setting it as such, even when the plating copper is formed in the solid form on the cured product of the composition, a curable resin composition capable of obtaining a cured product in which thermal expansion does not occur in the plated copper is obtained. Confirmed. Moreover, it was confirmed from the evaluation result of solder heat resistance that each composition of the Example was excellent in heat resistance and chemical-resistance, and can be used as a composition for wiring boards.

Sixth Embodiment

As cellulose nanocrystal particle CNC1 and CNC2, the thing of manufacture examples 4 and 5 similar to a 1st Example was used.

According to the description of the following Table 40, 41, after mixing and stirring each component, it was disperse | distributed repeatedly 6 times using the high-pressure homogenizer Nanovater NVL-ES008 of the Yoshida Kikai Kogyo Co., Ltd., and each composition was prepared. In addition, the numerical value in Table 40, 41 represents a mass part.

About each composition obtained by the Example and the comparative example, thermal expansion rate, heat resistance, insulation, toughness (elongation rate), and pot life were evaluated. The evaluation method is as follows.

[Coefficient of Thermal Expansion]

Each composition was apply | coated to the PET film with a thickness of 38 micrometers with the applicator of a gap of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Then, it crimped | bonded for 60 second on 60 degreeC and the pressure of 0.5 MPa on the copper foil of thickness 18micrometer with a vacuum laminator, laminated the resin layer of each composition, and peeled off the PET film. Subsequently, it heated in 180 degreeC for 30 minutes in the hot air circulation type drying furnace, hardened | cured, and peeled from copper foil, and obtained the film sample containing the hardened | cured material of each composition. The obtained film sample was cut into 3 mm width x 30 mm length, and it was set as the test piece for thermal expansion coefficient measurement. About this test piece, using TMA (Thermomechanical Analysis) Q400 manufactured by T-A Instruments Inc., the temperature was raised to 5 ° C./min from 20 mm to 250 ° C. in a chuck mode between the chuck to 16 mm, a load of 30 mN, and a nitrogen atmosphere. The temperature was lowered to 5 ° C./min to 250 to 20 ° C., and the coefficients of thermal expansion α 1 and α 2 (ppm / K) were measured. These measurement results are shown together in Tables 40 and 41.

[Heat resistance]

Each composition was apply | coated to the PET film with a thickness of 38 micrometers with the applicator of a gap of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Then, it crimped | bonded for 60 second on 60 degreeC and the pressure of 0.5 MPa on the copper foil of thickness 18micrometer with a vacuum laminator, laminated the resin layer of each composition, and peeled off the PET film. Subsequently, it heated in 180 degreeC for 30 minutes in the hot air circulation type drying furnace, hardened | cured, and peeled from copper foil, and obtained the film sample containing the hardened | cured material of each composition. After crushing the obtained film sample by the induction of agate agent, 3 weight% heating weight loss temperature was confirmed and evaluated from the TG curve measured under the temperature increase rate of 10 degree-C / min and nitrogen stream based on JIS-K-7120. . The evaluation criteria made (circle) and thing (310 degreeC or more) the thing whose 3 weight% heating weight loss temperature is less than 300 degreeC x and 300 degreeC or more and less than 310 degreeC (circle).

[Insulation]

Each composition was apply | coated to the PET film with a thickness of 38 micrometers with the applicator of a gap of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Subsequently, each composition was pressed for 60 seconds under a condition of 60 ° C. and a pressure of 0.5 MPa using a vacuum laminator on an A coupon of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm thick FR-4 substrate with a thickness of 35 μm copper. The resin layer was laminated, the PET film was peeled off, and heated at 180 ° C. for 30 minutes in a hot air circulation drying furnace to cure. Subsequently, the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 was cut to form an electrically independent terminal (cut at the dotted line in Figs. 6-4). And the bias of DC500V was applied so that the upper part of A coupon might be a cathode and a lower part might be an anode, and insulation resistance value was measured and evaluated.

(Circle) evaluation and the thing of insulation resistance value less than 100 G (ohm) made x into evaluation criteria. The evaluation results are shown in Tables 40 and 41 together.

[tenacity]

Each composition was apply | coated to the PET film of thickness 38micrometer with the applicator of 200 micrometers, and it dried for 20 minutes at 90 degreeC in the hot-air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Subsequently, an electrolytic copper foil having a thickness of 18 μm with the gloss side upward was fixed with a tape on a FR-4 copper clad laminate having a thickness of 1.6 mm, and the dry film was 60 ° C. under a vacuum laminator at 60 ° C. under a pressure of 0.5 MPa. The resin layer of each composition was laminated on the said electrolytic copper foil, then, PET film was peeled off, and it heated at 180 degreeC for 30 minutes in the hot-air circulation type drying furnace, and hardened the resin layer. And the fixed tape was peeled off, the electrolytic copper foil was peeled off, and the film sample containing a resin layer was obtained. Next, in accordance with JIS K7127, the film sample was cut to a predetermined size to prepare a test piece for evaluation. About this test piece, the stress [MPa] and the distortion [%] were measured at 10 mm / min of tensile velocity using the small benchtop testing machine EZ-SX by Shimadzu Corporation. Distortion [%] at this time is the elongation rate at the time of breaking a test piece, and since it can be evaluated that toughness is so large that it is high, toughness was evaluated from this distortion [%].

As for evaluation criteria, what made distortion [%] less than 2.0% x and what was 2.0% or more (circle). The evaluation results are shown in Tables 40 and 41 together.

[Available time]

The viscosity after dispersion of each composition was measured using the Toki Sangyo cornplate type viscometer TPE-100-H, and it was set as the initial viscosity. Then, it put in the container which can be sealed, it was left to stand at the temperature of 23 degreeC, the viscosity after 48 hours and 96 hours was measured and evaluated. As for evaluation criteria, (circle) and the increase rate after 48 hours were (triangle | delta), and the increase rate after 48 hours was 30% or more that the increase rate of the viscosity after 96 hours was 30% or less. As it is possible to be X, as use time is short, problem may occur if we do not perform the next process early when one liquid phase and film form are made into low temperature from low temperature storage, but it is possible that it is ○ because it is long Even if it is a film form then, it becomes easy to handle.

* 6-1) Thermosetting resin 6-1: Cyclohexanone varnish (cyclic ether compound having a naphthalene skeleton) of 50 mass% of solid content made by Epiclone HP-4032 DIC Co., Ltd.

* 6-2) Thermosetting resin 6-2: Cyclohexanone varnish (cyclic ether compound having a naphthalene skeleton) of NC-7300L Nippon Kayaku Co., Ltd. solid content 50 mass%

* 6-3) Thermosetting resin 6-3: Cyclohexanone varnish (cyclic ether compound which has an anthracene skeleton) of 50 mass% of solid content by YX-8800 Mitsubishi Chemical Corporation

* 6-4) Thermosetting resin 6-4: Cyclohexanone varnish (cyclic ether compound having a dicyclopentadiene skeleton) of 50% by mass of epiclon HP-7200 solid content

* 6-5) Thermosetting resin 6-5: Cyclohexanone varnish (cyclic ether compound which has a biphenyl skeleton) of 50 mass% of solid content by NC-3000H Nippon Kayaku Co., Ltd.

* 6-6) Thermosetting resin 6-6: Cyclohexanone varnish (cyclic ether compound which has a biphenyl skeleton) of 50 mass% of solid content by YX-4000 Mitsubishi Chemical Corporation

* 6-7) Thermosetting resin 6-7: cyclohexanone varnish of 50 mass% of solid content made by Epiclone N-740 DIC Co., Ltd.

* 6-8) Thermosetting resin 6-8: Epiclone 830 DIC Corporation

* 6-9) Thermosetting resin 6-9: manufactured by JER827 Mitsubishi Chemical Corporation

* 6-10) Phenoxy resin 6-1: Cyclohexanone varnish of 30 mass% of solid content by YX6954 Mitsubishi Chemical Corporation

* 6-11) Curing agent 6-1: 60 mass% cyclohexanone varnish by HF-1 Maya and Kasei Corporation

* 6-12) Curing agent 6-2: Bisphenol A diacetate Tokyo Kasei Kogyo Co., Ltd. agent (active ester)

* 6-13) Curing catalyst 6-1: 2E4MZ (2-ethyl-4-methylimidazole) manufactured by Shikoku Kasei Kogyo Co., Ltd.

* 6-14) Filler 6-1: Admafine SO-C2 Co., Ltd.

* 6-15) Organic Solvent 6-1: Dimethylformamide

* 6-16) Antifoam 6-1: BYK-352 Big Chemi Japan Co., Ltd.

* 6-17) Cellulose powder: NP fiber W-06MG (average particle diameter 6 µm) manufactured by Nippon Seishi

As apparent from the results shown in Tables 40 and 41, by using cellulose nanocrystal particles and fillers other than cellulose nanocrystal particles in combination, they maintain a low coefficient of thermal expansion not only at normal temperature but also at high temperatures at the time of component mounting, It was confirmed that hardened | cured material excellent in various characteristics, such as heat resistance and the like, can be obtained, and the curable resin composition excellent in the usable time is obtained. Although not shown in Tables 40 and 41, it was confirmed that the relative dielectric constant and dielectric loss tangent were reduced by using an active ester as a curing agent.

Seventh Example

[Production of Fine Cellulose Fibers]

Preparation Example 6 (CNF Dispersion 1)

After bleaching kraft pulp fiber (Machenzie CSF 650 ml by Fletcher Challenge Canada) of coniferous tree with agitation with 9900 g of ion-exchanged water, TEMPO (2,2,6,6-tetramethylpiperier made by ALDRICH) 1.25 mass% of din1-oxyl free radicals), 12.5 mass% of sodium bromide, and 28.4 mass% of sodium hypochlorite were added in this order. A pH stat was used and 0.5 M sodium hydroxide was added dropwise to maintain the pH at 10.5. After 120 minutes (20 degreeC) of reaction, dripping of sodium hydroxide was stopped and the oxidation pulp was obtained. Oxidized pulp obtained using ion-exchanged water was sufficiently washed and then dewatered. Thereafter, 3.9 g of oxidized pulp and 296.1 g of ion-exchanged water were subjected to two micronization treatments at 245 MPa using a high-pressure homogenizer (manufactured by Sugino Machine Co., Ltd., Starburst Laboratory HJP 2 5005) to form carboxyl group-containing fine cellulose fibers. The dispersion liquid (solid content concentration 1.3 mass%) was obtained.

Subsequently, 4088.75 g of the obtained carboxyl group-containing fine cellulose fiber dispersion was placed in a beaker, 4085 g of ion-exchanged water was added to an aqueous solution of 0.5% by mass, and stirred at room temperature (25 ° C.) for 30 minutes with a mechanical stirrer. Subsequently, 245g of 1M aqueous hydrochloric acid solution was added and reacted at room temperature for 1 hour. After completion of the reaction, the solution was reprecipitated with acetone, filtered, and then washed with acetone / ion exchanged water to remove hydrochloric acid and salt. Finally, acetone was added and filtered to obtain an acetone-containing acidic cellulose fiber dispersion (solid content concentration 5.0% by mass) in a state where the carboxyl group-containing fine cellulose fibers were swollen in acetone. After the reaction was completed, the mixture was filtered, and then washed with ion-exchanged water to remove hydrochloric acid and salt. And the dispersion liquid which solvent-substituted with acetone and adjusted solid content to 5.0 mass% was obtained. Subsequently, 250 g of Epiclone 830 DIC Corporation (bisphenol F type epoxy resin) and 100 g of JER827 Mitsubishi Chemical Co., Ltd. (bisphenol A type epoxy resin) and ELM100 Sumitomo Kagaku Kogyo Co., Ltd. (amines are used as precursors. Epoxy resin to be mixed: 250 g of triglycidylaminophenol) and 1000 g of a dispersion in which solvent substitution is carried out with the acetone and the solid content is adjusted to 5.0% by mass, acetone is removed by evaporation after stirring, and an epoxy resin-containing acid cellulose fiber dispersion (Average fiber diameter 3.3 nm, CNF density | concentration 7.7 mass%) was obtained.

Preparation Example 7 (CNF Dispersion 2)

After bleaching kraft pulp fiber (Machenzie CSF 650 ml by Fletcher Challenge Canada) of coniferous tree with agitation with 9900 g of ion-exchanged water, TEMPO (2,2,6,6-tetramethylpiperier made by ALDRICH) 1.25 mass% of din1-oxyl free radicals), 12.5 mass% of sodium bromide, and 28.4 mass% of sodium hypochlorite were added in this order. A pH stat was used and 0.5 M sodium hydroxide was added dropwise to maintain the pH at 10.5. After 120 minutes (20 degreeC) of reaction, dripping of sodium hydroxide was stopped and the oxidation pulp was obtained. Oxidized pulp obtained using ion-exchanged water was sufficiently washed and then dewatered. Thereafter, 3.9 g of oxidized pulp and 296.1 g of ion-exchanged water were subjected to two micronization treatments at 245 MPa using a high-pressure homogenizer (manufactured by Sugino Machine Co., Ltd., Starburst Laboratory HJP 2 5005) to form carboxyl group-containing fine cellulose fibers. The dispersion liquid (solid content concentration 1.3 mass%) was obtained.

Subsequently, 4088.75 g of the obtained carboxyl group-containing fine cellulose fiber dispersion was placed in a beaker, 4085 g of ion-exchanged water was added to an aqueous solution of 0.5% by mass, and stirred at room temperature (25 ° C.) for 30 minutes with a mechanical stirrer. Subsequently, 245g of 1M aqueous hydrochloric acid solution was added and reacted at room temperature for 1 hour. After completion of the reaction, the solution was reprecipitated with acetone, filtered, and then washed with acetone / ion exchanged water to remove hydrochloric acid and salt. Finally, acetone was added and filtered to obtain an acetone-containing acidic cellulose fiber dispersion (solid content concentration 5.0% by mass) in a state where the carboxyl group-containing fine cellulose fibers were swollen in acetone. After the reaction was completed, the mixture was filtered, and then washed with ion-exchanged water to remove hydrochloric acid and salt. After solvent substitution with acetone, solvent substitution was carried out with DMF, and the DMF containing acidic cellulose fiber dispersion liquid (average fiber diameter 3.3nm, solid content concentration 5.0 mass%) of the carboxyl group-containing fine cellulose fiber swelled was obtained.

400 g of the obtained DMF-containing acidic cellulose fiber dispersion and 3 g of hexylamine were placed in a beaker equipped with a magnetic stirrer and a stirrer, and dissolved in 3000 g of ethanol. The reaction solution was reacted at room temperature (25 ° C) for 6 hours. After completion | finish of reaction, it filtered and wash | cleaned and solvent-substituted with DMF, and obtained the fine cellulose fiber composites (5.0 mass% of solid content concentration) which the amine connected to the fine cellulose fiber through the ionic bond. Subsequently, 25 g of Epiclone 830 DIC Co., Ltd. (bisphenol F type epoxy resin) and 10 g of JER827 Mitsubishi Chemical Co., Ltd. (bisphenol A type epoxy resin) and ELM100 Sumitomo Chemical Co., Ltd. (amines are used as precursors. Epoxy resin to be mixed: 25 g of triglycidylaminophenol) and 200 g of a fine cellulose fiber composite in which an amine is linked to the fine cellulose fiber through an ionic bond, and after stirring, DMF is removed by an evaporator, and fine cellulose containing an epoxy resin is contained. The fine cellulose fiber composites (CNF concentration 15.4 mass%) in which amine was connected to the fiber through the ionic bond was obtained.

The CNF produced by the method of Production Example 7 has particularly good dispersibility and can be dispersed by a general method without using a special disperser such as a high pressure homogenizer.

Preparation Example 8 (CNF Dispersion 3)

10 mass% of fine cellulose fibers (BiNFi-s by Sugino Machine Co., Ltd., 80 nm of average fiber diameters) were dehydrated and filtered, 10 times of acetone of the mass of a filtrate was added, and it filtered, after stirring for 30 minutes. This substitution operation was repeated 3 times, 20 times the amount of acetone of the mass of a filtrate was added, and the fine cellulose fiber dispersion liquid (solid content concentration 5.0 mass%) was produced. Subsequently, 250 g of Epiclone 830 DIC Corporation (bisphenol F type epoxy resin) and 100 g of JER827 Mitsubishi Chemical Co., Ltd. (bisphenol A type epoxy resin) and ELM100 Sumitomo Kagaku Kogyo Co., Ltd. (amines are used as precursors. 250 g of epoxy resins to be added: triglycidylaminophenol and 1000 g of the fine cellulose fiber dispersion were mixed, and after stirring, acetone was removed by an evaporator to obtain a cellulose fiber dispersion (CNF concentration 7.7% by mass) containing an epoxy resin. .

Preparation Example 9 (CNC Dispersion 1)

The portrait sheets of dried coniferous bleached kraft pulp were treated with a cutter mill and a pin mill to obtain a cotton fiber. 100 g of this cotton fiber was taken as an absolute dry mass, suspended in 2 L of 64% sulfuric acid aqueous solution, and hydrolyzed at 45 degreeC for 45 minutes.

After the obtained suspension was filtered, 10 L of ion-exchanged water was injected, stirred and uniformly dispersed to obtain a dispersion. Subsequently, the process of filtration dehydration was repeated 3 times with respect to the said dispersion liquid, and the dehydration sheet was obtained. Subsequently, the obtained dehydration sheet was diluted with 10 L of ion-exchanged water, the aqueous solution of 1N sodium hydroxide was added little by little, stirring, and it was set as about pH12. Then, this suspension was filtered and dewatered, 10 L of ion-exchange water was added, and the process of stirring and filtering and dehydrating was repeated twice.

Subsequently, ion-exchanged water was added to the obtained dewatering sheet to prepare a 2% suspension. This suspension was passed 10 times by the pressure of 245 MPa with the wet granulation apparatus ("Altimizer" by Sugino Machine Co., Ltd.), and the cellulose nanocrystal particle aqueous dispersion was obtained.

Thereafter, the solvent was substituted with acetone to obtain an acetone dispersion (solid content concentration of 5.0% by mass) in a state where the cellulose nanocrystal particles were swollen. As a result of observing and measuring the cellulose nanocrystal particle in the obtained dispersion liquid by AFM, the average crystal width was 10 nm and the average crystal length was 200 nm.

Subsequently, 50 g of Epiclone 830 DIC Co., Ltd. (bisphenol F type epoxy resin) and 20 g of JER827 Mitsubishi Chemical Co., Ltd. (bisphenol A type epoxy resin) and ELM100 Sumitomo Kagaku Kogyo Co., Ltd. (amines are used as precursors. 50 g of an epoxy resin to be made: triglycidylaminophenol) and 200 g of the acetone dispersion were added, and after stirring, acetone was removed by an evaporator to obtain an epoxy resin-containing acidic cellulose fiber dispersion.

Preparation Example 10 (CNC Dispersion 2)

100 g of cotton wool (manufactured by Hakujuji Co., Ltd.) was taken as an absolute dry mass, suspended in 2 L of a 64% sulfuric acid aqueous solution, and hydrolyzed at 45 ° C for 45 minutes.

After the obtained suspension was filtered, 10 L of ion-exchanged water was injected, stirred and uniformly dispersed to obtain a dispersion. Subsequently, the process of filtration dehydration was repeated 3 times with respect to the said dispersion liquid, and the dehydration sheet was obtained. Subsequently, the obtained dehydration sheet was diluted with 10 L of ion-exchanged water, the aqueous solution of 1N sodium hydroxide was added little by little, stirring, and it was set as about pH12. Then, this suspension was filtered and dewatered, 10 L of ion-exchange water was added, and the process of stirring and filtering and dehydrating was repeated twice.

Subsequently, ion-exchanged water was added to the obtained dewatering sheet to prepare a 2% suspension. This suspension was passed 10 times by the pressure of 245 MPa with the wet granulation apparatus ("Altimizer" by Sugino Machine Co., Ltd.), and the cellulose nanocrystal particle aqueous dispersion was obtained.

Thereafter, the solvent was substituted with acetone to obtain an acetone dispersion (solid content concentration of 5.0% by mass) in a state where the cellulose nanocrystal particles were swollen. As a result of observing and measuring the cellulose nanocrystal particle in the obtained dispersion liquid by AFM, the average crystal width was 7 nm and the average crystal length was 150 nm.

Subsequently, 50 g of Epiclone 830 DIC Co., Ltd. (bisphenol F type epoxy resin) and 20 g of JER827 Mitsubishi Chemical Co., Ltd. (bisphenol A type epoxy resin) and ELM100 Sumitomo Kagaku Kogyo Co., Ltd. (amines are used as precursors. 50 g of an epoxy resin to be made: triglycidylaminophenol) and 200 g of the acetone dispersion were added, and after stirring, acetone was removed by an evaporator to obtain an epoxy resin-containing acidic cellulose fiber dispersion.

According to the description of the following Tables 42 and 43, after mixing and stirring each component, using Yoshida Kikai Kogyo High Pressure Homogenizer Nanovater NVL-ES008 was repeatedly dispersed six times to prepare each composition. In addition, the numerical value in Table 42, 43 represents a mass part.

[Smear around through hole]

Electroless copper plating, electrolytic copper plating, electrolytic copper plating, electrolytic copper plating, electrolytic copper plating, electrolysis copper plating, electroplating The test board | substrate was processed in order of the copper plating process, and the copper plating process of 25 micrometers of copper thicknesses on the surface of the copper clad laminated board was prepared. After buffing the test substrate, each composition was filled into the through hole by screen printing using a plate having a circular opening having a diameter of 0.9 mm in the portion of the hole, and then after filling, into a hot air circulating drying furnace, and 120 Precuring was performed at 1 degreeC for 1 hour, and the test piece was obtained. The test piece was observed with the magnifying glass, and the state of the bleeding of the hardened | cured material was evaluated. The evaluation criteria evaluated that bleeding was not completely seen, and there was no bleeding bleeding, but wider than the size of the plate. It was. The results are shown in Tables 42 and 43.

[Abrasiveness]

About the test piece which evaluated the bleeding around the through-hole, abrasiveness was evaluated by buff grinding (# 320). In observation using a magnifying glass, the thing which hardened | cured material disappeared completely was made into (circle) and what needed 2 or more times at x. The results are shown in Tables 42 and 43.

[Inflated marks on through holes]

About the test piece which evaluated abrasiveness, it processed in order of electroless copper plating (through cup PEA, the Uemura Kogyo Co., Ltd.), electrolytic copper plating process (copper thickness 10 micrometers). Subsequently, after passing three times through the reflow furnace of the peak temperature of 265 degreeC, the part on a hole was visually evaluated. (Circle) that there was no expansion mark on 15 through holes, (triangle | delta) that an expansion mark was seen on 1-5 through-holes, (triangle | delta), and what showed an expansion mark to 6 or more through holes were made into x. The results are shown in Tables 42 and 43.

Since Examples 7-1 to 7-4 contain thermosetting resins 7-1 to 7-3 in the CNF dispersion, the resin powder is almost the same in both the Examples and Comparative Examples.

* 7-1) Thermosetting resin 7-1: Epiclone 830 DIC Corporation (bisphenol F type epoxy resin)

* 7-2) Thermosetting resin 7-2: jER827 Mitsubishi Chemical Co., Ltd. make (bisphenol-A epoxy resin)

* 7-3) Thermosetting resin 7-3: Sumiepoxy ELM100 Sumitomo Kagaku Kogyo Co., Ltd. product (epoxy resin using amines as a precursor: triglycidylaminophenol)

* 7-4) Thermosetting resin 7-4: Denacol EX-212 Nagase Chemtex Co., Ltd. (1,6 hexanediol diglycidyl ether)

* 7-5) Curing agent 7-1: 2MZA-PW Shikoku Kasei Kogyo Co., Ltd. make (2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-S-tri Ajin)

* 7-6) Preservation stabilizer 7-1: Cure duct L-07N Shikoku Kasei Kogyo Co., Ltd. product (mixture of 5 mass% boric acid ester, an epoxy resin, and a novolak resin)

* 7-7) Inorganic filler 7-1: Soften 1800 Bihoku Hunka Kogyo Co., Ltd. (calcium carbonate)

* 7-8) Antifoam 7-1: Made by KS-66 Shin-Etsu Kagaku Kogyo Co., Ltd.

As is apparent from the results shown in Tables 42 and 43, by using the curable resin composition in which fine powder such as fine cellulose fibers is dispersed in the resin filler, expansion occurs on the holes filled with holes even in heating during component mounting. In addition, it was confirmed that the hole filling material which does not generate a bleeding of a resin component and does not produce the recessed part of a hole also in a grinding | polishing process is obtained.

1, 3, 8, 11: conductor pattern
2: core substrate
1a, 4: connection part
5: through hole
6, 9: interlayer insulation layer
7, 10: Via
12: solder resist layer
101: wiring board
102: description
103: plated through hole
104: conductor circuit layer
105: precured product or the main cured product of the curable resin composition
106: conductor circuit layer
107: multilayer printed wiring board with build-up layer laminated on core board
108: buildup layer
109: conductor circuit layer
110: When forming a build-up layer, the via-hole was formed in the hole and the multilayer printed wiring board which was embedded with the hardened | cured material of curable resin composition.
111: Via hole embedded with cured product of curable resin composition
112: Residues around the perforations that may occur in the polishing process
113: recesses in the holes that may occur in the polishing process

Claims (18)

Curable resin, At least one dimension contains fine powder smaller than 100 nm, and the filler other than this fine powder, Curable resin composition characterized by the above-mentioned. The curable resin composition according to claim 1, wherein the fine powder is fine cellulose powder. The curable resin composition according to claim 1, wherein the fine powder is cellulose nanocrystal particles. The curable resin composition of Claim 1 whose compounding ratio in all the fillers of the said fine powder and fillers other than this fine powder is (filler: fine powder other than fine powder) = 100: (0.04-30) by mass ratio. The curable resin composition according to any one of claims 1 to 4, wherein the curable resin contains a cyclic ether compound having at least one kind of a naphthalene skeleton and an anthracene skeleton. The said curable resin contains at least 1 sort (s) selected from the group which consists of a cyclic ether compound which has a dicyclopentadiene frame | skeleton, and a phenol resin which has a dicyclopentadiene frame | skeleton. Curable resin composition. The curable resin composition according to any one of claims 1 to 4, wherein the curable resin contains a phenoxy resin. The curable resin composition according to any one of claims 1 to 4, wherein the curable resin comprises at least one member selected from the group consisting of a cyclic ether compound having a biphenyl skeleton and a phenol resin having a biphenyl skeleton. . The curable resin composition of Claim 1 has a resin layer apply | coated and dried on a film, The dry film characterized by the above-mentioned. The said resin layer of the curable resin composition of Claim 1 or the dry film of Claim 9 is hardened | cured, The hardened | cured material characterized by the above-mentioned. The hardened | cured material of Claim 10 is provided, The electronic component characterized by the above-mentioned. As curable resin composition for filling in at least one of a recessed part and a through hole of a printed wiring board,
(A) fine powder at least one dimension smaller than 100 nm,
(B) thermosetting components
Curable resin composition comprising a. The curable resin composition of Claim 12 containing the cyclic ether compound which uses amine as a precursor as said (B) thermosetting component. The curable resin composition according to claim 12, comprising a bisphenol A type epoxy resin and a bisphenol F type epoxy resin as the thermosetting component (B). Curable resin composition of Claim 12 containing (C) boric acid ester compound. Curable resin composition of Claim 12 containing (D) filler other than said (A) fine powder. Hardened | cured material formed by hardening | curing curable resin composition of Claim 12. At least one of the recessed part and the through hole of a printed wiring board is filled with the hardened | cured material of Claim 17, The printed wiring board characterized by the above-mentioned.

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