TW201903039A - Curable resin composition, dry film, cured product, electronic parts, and printed wiring board - Google Patents

Abstract

The present invention provides: a curable resin composition with which it is possible to obtain a cured product that is capable of retaining a low thermal expansion rate even in a high-temperature range during component mounting and that exhibits various excellent properties such as toughness; and a dry film, a cured product, and an electronic component using the curable resin composition. The curable resin composition comprises a curable resin, a fine powder in which at least one of the dimensions is smaller than 100 nm, and a filler other than the fine powder. The dry film, the cured product and the electronic component are obtained by using said curable resin composition.

Description

Curable resin composition, dry film, cured product, electronic component, and printed wiring board

The present invention relates to a curable resin composition, a dry film, a cured product, and an electronic component. The present invention also relates to a curable resin composition, a cured product, and a printed wiring board.

Examples of the electronic component include a wiring board, and active or driven parts fixed to the wiring board. In the wiring board, there are those who apply conductive wiring to an insulating substrate and connect and fix active parts, driven parts, and the like. Depending on the application, the insulating layer and the conductive layer may be multilayered, or elastic insulation may be used. The substrate becomes an important electronic component in electronic equipment. In addition, the wiring board is also used for semiconductor packaging, and the curable resin composition or dry film for the wiring board is used as an outer layer after the wiring board or the semiconductor is mounted. Examples of active parts and driven parts include transistors, diodes, resistors, coils, and condensers.

In recent years, with the miniaturization of electronic devices, the required characteristics of electronic components have become stricter. Regarding wiring boards, high-density wiring is gradually required. In order to ensure the reliability of wiring or component connection parts, the materials of wiring boards are gradually required to have low thermal expansion. Active components and driven components are also required to be miniaturized and highly integrated. Similarly, in order to ensure reliability, low thermal expansion properties are gradually required.

As a method for achieving a low thermal expansion property, for example, Patent Document 1 proposes a method for filling an inorganic filler in a resin and obtaining a low thermal expansion ratio.

In addition, as a means for achieving the low thermal expansion of such a material, for example, a method has been proposed in which cellulose fibers are used as a fiber-reinforced composite material (see Patent Document 2).

Furthermore, in recent years, with the miniaturization of electronic devices, in order to transmit high frequencies efficiently, electronic components have been required to have low dielectric characteristics. As a method for achieving low dielectric characteristics, for example, Non-Patent Document 1 proposes a method for reducing the relative permittivity and the loss factor by using an epoxy resin having a dicyclopentadiene skeleton.

Furthermore, in recent years, with the increase in the performance of electronic devices, higher frequencies than before have been required, and electronic components have been required to efficiently transmit high frequencies. As a characteristic of high frequency, a surface effect is mentioned. For example, Non-Patent Document 2 describes that as the frequency becomes higher, a current can only pass near the surface of the conductor.

In addition, in recent years, in order to cope with the miniaturization and high performance of devices equipped with printed wiring boards, lighter, thinner and shorter printed wiring boards are being evolved. Therefore, the conductor circuits of printed wiring boards are required to be thinner and the mounting area reduced. In contrast, in a method for manufacturing a printed wiring board, a resin filler is filled in a recessed portion or a through hole provided in a through hole or a through hole of the wiring board to harden it, grind it to a smooth surface, and then fill it with the relevant resin filler. Insulation layers and conductor layers are further assembled on through-holes or through-holes, and a multilayer method is widely used. As a resin filler used in such a construction method, a material excellent in various properties such as filling properties of recesses or through holes, abrasiveness or heat resistance of hardened materials is required, and a thermosetting resin composition such as Patent Document 3 is proposed. .

On the other hand, for the purpose of higher density, a method of mounting components such as conductor pads or through-holes on recesses or through-holes filled with resin fillers or through-holes has recently been adopted. Prior Art Literature Patent Literature

Patent Document 1: JP 2001-72834 Patent Document 2: JP 2011-001559 Patent Document 3: JP 2015-10146 Non-Patent Document

Non-Patent Document 1: "Journal of network polymer" Vol. 17, No. 2 (1996) pp69 Non-Patent Document 2: "Physics Education" Vol. 61 No. 1 (2013) pages 18-20

Problems to be Solved by the Invention

However, in the material described in Patent Document 1, in order to obtain a desired low thermal expansion coefficient, a large amount of inorganic filler must be filled, and there is a problem that the physical properties of the hardened material such as toughness are deteriorated. Further, the present inventors have found that among the materials described in Patent Document 1, if the temperature exceeds 200 ° C when the component is mounted, the temperature expansion region will have a large thermal expansion coefficient. In order to ensure reliability, a new problem arises that it has no effect. Here, a first object of the present invention is to provide a hardenable resin composition which can maintain a low thermal expansion coefficient even in a high-temperature region at the time of component mounting, and can obtain a hardened material having various properties such as toughness. .第一 A first other object of the present invention is to provide a dry film, a cured product, and an electronic component using the curable resin composition.

In addition, since the material described in Patent Document 2 is a fiber having an average fiber diameter of 4 to 200 nm dispersed in a matrix material, a composite material with low thermal expansion can be obtained. However, in the method described in this Patent Document 2, cellulose fibers are selected in order to further improve the low thermal expansion property. On the other hand, the inventors have found out that the purpose is to reduce the size, density, and accumulation. In the case of laminated electronic components, there is a new problem that the reliability of the insulation between the layers deteriorates. Here, a second object of the present invention is to provide a curable resin composition which can be obtained as an electronic component having a laminated structure with a low thermal expansion property and the purpose of miniaturization, high density, and high accumulation. Hardened product with excellent interlayer insulation reliability.第二 A second additional object of the present invention is to provide a dry film, a cured product, and an electronic component using the curable resin composition.

Furthermore, in the high frequency of electronic components, it is important not only to have low dielectric characteristics but also to form high-definition circuits. In this regard, although the low-dielectric characteristics can be obtained in the insulating layer described in Non-Patent Document 1, the present inventors have found that the adhesion strength with a high-definition circuit (plated copper) cannot be obtained. In view of this, a third object of the present invention is to provide a hardenable resin composition which can obtain a hardened material having low dielectric properties and a good adhesion between the hardened material and the plated copper. Furthermore, a third additional object of the present invention is to provide a dry film, a cured product, and an electronic component using the curable resin composition.

Furthermore, the above-mentioned surface effect means that it can be expressed even in the wiring of electronic parts, and that high frequency only passes through the extreme surface of the wiring. Therefore, in order to efficiently transmit a high frequency, it is considered to smooth the interface between the wiring of the electronic component and the insulating material. However, if such smoothing is performed, there is a problem that the adhesion (peel strength) with the plated copper constituting the insulating material and wiring is reduced. On the other hand, in order to improve the adhesion of the plated copper constituting the wiring, generally, when a laser is used to dig an insulating material, the stains generated at the bottom are removed (decontaminated). Roughen the surface of the insulating material. However, if such a roughening is performed, there is a problem that a high frequency cannot be transmitted efficiently. Here, a fourth main object of the present invention is to provide a curable resin composition which can remove stains generated by laser processing in a stain removal step, and can also obtain a small surface roughness that is advantageous for high-frequency transmission. , And the peeling strength is also better hardened. Furthermore, a fourth additional object of the present invention is to provide a dry film, a cured product, and an electronic component using the curable resin composition.

Furthermore, with the material described in Patent Document 2, since a fiber having an average fiber diameter of 4 to 200 nm is dispersed in a matrix material, a composite material with low thermal expansion can be obtained. However, the inventors have found that in the above-mentioned composite material, if the plated copper is formed into a solid state on the material, a new problem arises in that the plated copper swells due to the thermal history of parts mounting and the like. Here, a fifth main object of the present invention is to provide a curable resin composition which can obtain low thermal expansion properties, and even if copper plating is applied for the purpose of manufacturing wiring on the hardened material of the composition, in addition to wiring When the plated copper is formed into a solid state for the purpose of electromagnetic wave shielding other than the pattern, a hardened material that does not expand the plated copper due to thermal history and is excellent in high temperature resistance can be obtained.第五 A fifth other object of the present invention is to provide a dry film, a cured product, and an electronic component using the curable resin composition.

Furthermore, in the material described in Patent Document 1, in order to obtain a desired low thermal expansion coefficient, a large amount of an inorganic filler must be filled, and there is a problem that physical properties of hardened materials such as toughness are deteriorated. Further, the present inventors have found that among the materials described in Patent Document 1, if the component exceeds 200 ° C in the temperature range at the time of mounting, there is a large thermal expansion coefficient, and in order to ensure reliability, a new problem arises that it has no effect.

Here, a sixth object of the present invention is to provide a curable resin composition capable of obtaining a low thermal expansion coefficient even in a high-temperature region at the time of component mounting, and having excellent properties such as toughness and heat resistance. Of hardened.第六 A sixth other object of the present invention is to provide a dry film, a cured product, and an electronic component using the curable resin composition.

Furthermore, if the thermosetting resin composition as described in Patent Document 3 is used as a resin filler with respect to the above-mentioned method used in the method for manufacturing a printed wiring board, the following problem arises: through holes filled with the resin filler The metal wiring such as a recessed part such as a through hole or a conductive pad or a through hole on the through hole will expand during the high-temperature heating step during component mounting. Such expansion will affect reliability. In addition, the resin composition of a thermosetting resin composition filled in a recessed portion or a through hole (hereinafter simply referred to as “hole portion and the like”) is melted and hardened by heating. Therefore, there may be problems such as bleeding out of the hole portion and the like during curing . The filler component of the exuded resin composition will be thinner. Due to its adhesiveness, it cannot be completely removed and remained in the next step of grinding, which is the cause of the poor conditions of plating. Furthermore, in the grinding step after curing of the thermosetting resin composition filled in the recessed portion or the through hole, leakage of the resin filler around the hole portion and the like must be completely removed. As a result, the hole portion and the like may be excessively polished due to excessive grinding. Depression is another problem that cannot be a complete smooth surface.

Here, a seventh main object of the present invention is to provide a curable resin composition capable of solving the above-mentioned problems, and in particular, to provide a curable resin composition, which is used even in a high-temperature heating step during component mounting, Recesses such as through-holes or through-holes filled with resin fillers or conductor pads or through-holes on through-holes do not swell, and there is no resin composition with thinner filler components when hardened. In the polishing step after hardening, no dents such as holes caused by excessive polishing for smoothing are generated.第七 A seventh other object of the present invention is to provide a hardened material of a hardenable resin composition capable of solving the above-mentioned problems, and a printed wiring board filled with the hardened material, such as holes. Solutions to problems

As a result of meticulous research, the inventors have found that compared with conventional silicon dioxide or calcium carbonate, barium sulfate, talc, and oxidation used as filler materials for electronic component materials such as solder resists, interlayer insulation materials, and buried hole materials. A filler such as titanium is blended with a fine powder (hereinafter simply referred to as a "fine powder") having a size smaller than 100 nm at a time, which can unexpectedly solve the above problems and further solve the present invention.

That is, the curable resin composition of the first aspect of the present invention is characterized by containing a curable resin, a fine powder having a size of at least one order of less than 100 nm, and a filler other than the fine powder.

In the present invention, it is more suitable to use fine cellulose powder (hereinafter simply referred to as "CNF") or cellulose nanocrystalline particles (hereinafter simply referred to as "CNC") as the fine powder. In addition, the blending of the aforementioned fine powder with a filler other than the fine powder in a full filler is more preferably a mass ratio (filler other than the fine powder: fine powder) = 100: (0.04 ~ 30).

In the present invention, the curable resin includes a cyclic ether compound having at least one of a naphthalene skeleton and an onion skeleton, or a cyclic ether compound selected from a cyclic ether compound having a dicyclopentadiene skeleton and a dicyclopentadiene skeleton. It is preferable that at least one kind of the phenol resin is contained, or at least one kind is selected from the group consisting of a phenoxy resin, or a cyclic ether compound having a biphenyl skeleton and a phenol resin having a biphenyl skeleton.

The dry film of the present invention is characterized by having a resin layer obtained by coating and drying the curable resin composition on a film.

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.

An electronic component of the present invention is characterized by including the above-mentioned hardened material.

Herein, in the present invention, the cellulose nanocrystalline particles mean those in which cellulose raw materials are hydrolyzed with a high concentration of mineral acids (hydrochloric acid, sulfuric acid, hydrobromic acid, etc.) to remove the non-crystalline portion and separate only the crystalline portion. Specifically, it is not included in the hydrolysis obtained by applying a strong acid of 7 wt% or more, preferably 9 wt% or more, more preferably a strong acid such as sulfuric acid with a high concentration and a concentration of 60 wt% or more. Amorphous crystals.

In addition, as a result of meticulous research in the face of the above-mentioned problems, the present inventors have newly discovered that as a filling material for recesses or through-holes such as through-holes or through-holes of printed wiring boards, at least one time the element size is smaller than 100 nm A curable resin composition in which a fine powder and a thermosetting component are dispersed can solve the above-mentioned problems and complete the present invention.

The second type of the curable resin composition of the present invention is a curable resin composition used to fill at least one side of a recessed portion and a through hole of a printed wiring board, and is characterized by including (A) at least one time. Fine powder smaller than 100nm, and (B) thermosetting component.

In the curable resin composition of the present invention, as the thermosetting component (B), a cyclic ether compound containing an amine as a precursor is preferable, and a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are included. Resin is preferred.

The curable resin composition of the present invention preferably contains (C) a borate compound.

The curable composition of the present invention preferably contains a filler (D) other than the fine powder (A).

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 side of the recessed portion and the through hole of the printed wiring board is filled with the curable resin composition.

Herein, in the present invention, as the fine powder, especially the shape is not limited, and shapes such as fibrous, scaly, and granular can be used. "At least one-dimensional element is smaller than 100 nm" means primary, secondary, and cubic Either is smaller than 100nm. For example, in the case of a fibrous fine powder, there are those whose secondary element is smaller than 100 nm and which has a diffusion to the remaining primary elements. When the scale is a fine powder, one side is smaller than 100 nm. In addition, those who have a diffusion of the remaining secondary elements are granular fine powders, and those whose tertiary elements are smaller than 100 nm are mentioned. In the present invention, the size of the primary, secondary, and tertiary elements in the fine powder can be SEM (Scanning Electron Microscope; Scanning Electron Microscope), TEM (Transmission Electron Microscope), or AFM (Atomic Force). Microscope; atomic force microscope), etc. to observe and measure the fine powder. For example, in the case of scaly fine powder, the average value of the smallest one-dimensional thickness is measured, and the average thickness is set to be smaller than 100 nm. Specifically, at the diagonal line of the microscope photograph, 12 points of fine powders in the vicinity of which can be measured at random are randomly extracted, and the thickest fine powder and the thinnest fine powder are removed, and the remaining A thickness of 10 points is taken as an average value smaller than 100 nm. When is a fibrous fine powder, the average value of the smallest two-dimensional fiber diameter (hereinafter simply referred to as "average fiber diameter") is measured, and this average fiber diameter is made smaller than 100 nm. Specifically, at the diagonal drawing line of the microscope photograph, 12 points of fine powders in the vicinity are randomly extracted, the thickest fiber diameter and the thinnest fiber diameter are removed, and the remaining 10 fiber diameters are measured as The average is smaller than 100nm. When is a granular fine powder, the average value of the particle diameter is measured, and this average particle diameter is made smaller than 100 nm. Specifically, at the diagonal line of the microscope photograph, 12 points of fine powders in the vicinity are randomly selected, the maximum particle diameter and the minimum particle diameter are removed, and the remaining 10 particle diameters are measured as the average value. Less than 100nm. (2) In a fine powder having fibrous or scaly diffusion with other dimensions, the diffusion is, for example, less than 1000 nm, preferably less than 650 nm, and more preferably less than 450 nm. If the diffusion is less than 1000 nm, the reinforcing effect due to the mutual effect of the fine powders cannot be effectively obtained. In the present invention, the definition of the fine cellulose powder is the same as the fine powder. Invention effect

First, according to the present invention, a hardenable resin composition can be obtained, which can obtain a hardened product that can maintain a low thermal expansion coefficient even in a high-temperature region at the time of component mounting and is excellent in various properties such as toughness. Furthermore, according to the present invention, it is possible to provide a dry film, a cured product, and an electronic component using the curable resin composition.

Secondly, according to the present invention, it is possible to provide a hardenable resin composition, which can be obtained as a laminated structure of electronic components with low thermal expansion and miniaturization, high density, and high accumulation. A hardened product with excellent reliability. Furthermore, according to the present invention, it is possible to provide a dry film, a cured product, and an electronic component using the curable resin composition.

Third, according to the present invention, it is possible to provide a hardenable resin composition which can obtain a hardened product having low dielectric properties and a good adhesion between the hardened material and the plated copper. Furthermore, according to the present invention, it is possible to provide a dry film, a cured product, and an electronic component using the curable resin composition.

Fourth, by the present invention, it is possible to provide a hardenable resin composition which can be obtained in the spot removal step and can be removed by laser processing while having a small surface roughness which is advantageous for high-frequency transmission, and also has a peeling strength. Excellent hardened material. Furthermore, according to the present invention, it is possible to provide a dry film, a cured product, and an electronic component using the curable resin composition.

Fifth, with the present invention, it is possible to provide a curable resin composition which can obtain low thermal expansion and is provided with copper plating even for the purpose of producing wiring on the hardened material of the composition, in addition to the wiring pattern. When the plated copper is formed into a solid state for the purpose of shielding electromagnetic waves, a hardened material that does not expand the plated copper due to thermal history and is excellent in high temperature resistance can be obtained. Furthermore, according to the present invention, a dry film, a cured product, and an electronic component using the curable resin composition can be provided.

Sixth, according to the present invention, it is possible to provide a hardening resin composition having an excellent service life, which can obtain various properties such as toughness and heat resistance while maintaining a low thermal expansion coefficient even in a high-temperature region at the time of component mounting. Excellent hardened material. Furthermore, according to the present invention, it is possible to provide a dry film, a cured product, and an electronic component using the curable resin composition.

Seventh, according to the present invention, it is possible to provide a hardenable resin composition which is filled with a resin filler in a printed wiring board having at least one of a recessed portion and a through hole, even in a high-temperature heating step during component mounting. Recesses such as through-holes or through-holes, or conductor pads or through-holes on through-holes will not swell, and will not ooze out resin compositions with thinner filler components when hardened, and the grinding step after hardening will also No depressions such as pores caused by excessive polishing for smoothing. Furthermore, according to the present invention, it is possible to provide a printed wiring board in which a cured product of a curable resin composition capable of solving the above-mentioned problems and a hole portion are filled with the cured product.

Embodiment of the invention

Hereinafter, embodiments of the present invention will be described in detail.

<<< First Form of the Present Invention >> 最大 The hardening resin composition of the first form of the present invention is characterized by using a fine powder and a filler other than the fine powder as a filler.作为 With such a structure, regarding the first object, it is possible to provide a hardened material which can maintain a low thermal expansion coefficient even in a temperature range at the time of mounting a part exceeding 200 ° C, and is excellent in various properties such as toughness.

[Fine powder] 之 The fine powder used in the present invention means a powder having a size smaller than 100 nm at least once. As mentioned above, not only the powder is close to a fine sphere, but also a fiber having a cross-sectional diameter smaller than 100 nm, or a thickness. Those having a sheet shape (scale) smaller than 100 nm. Such a fine powder has a surface area per unit mass that is much larger than that of any three-dimensional one that is 100 nm or more, and the atomic ratio of the exposed surface increases. Therefore, it is thought that the mutual effect of the fine powders pulling each other will be obtained, and the reinforcing effect will be exhibited to reduce the thermal expansion property.

The fine powder may be particles having a size smaller than 100 nm at least once. The material is not particularly limited, and two or more kinds may be used in combination. Examples of the fine powder include carbons such as graphite, graphene, fullerene, single-layered carbon nanotubes, multilayered carbon nanotubes, silver, gold, iron, nickel, titanium oxide, cerium oxide, and zinc oxide. , Inorganic systems such as silicon dioxide and aluminum hydroxide, mineral systems such as clay, expansive stone, bentonite, or fine cellulose powder that opens plant fibers and fibers that separate only the crystalline part from cellulose raw materials Macromolecular systems such as sun-nano crystal particles, fine chitin that has been fibrillated with chitin obtained from crustaceans, and fine butyl glycans such as these fine chitin further subjected to alkali treatment, etc. can also be processed into these Nanotubes, nanowires, nanoflakes, or two or more types can be used together. Among these, as the hydrophilic fine powder, there are metal oxide fine particles such as titanium oxide, metal water oxide fine particles such as aluminum hydroxide, mineral fine particles such as white clay, fine cellulose fibers, and fine carapace. Su et al. Among such fine powders, a fine cellulose powder is preferable from the viewpoint of reinforcing effect and ease of operation, or from the viewpoint of adhesion improvement effect and ease of operation with plated copper. Moreover, cellulose nanocrystalline particles are also preferable.

The inventors focused on the fine cellulose powder as a powder having a size smaller than 100 nm at least once, and compared the relationship between the blending amount and the thermal expansion coefficient with silicon dioxide and studied it in detail. With a small amount of powder, a new phenomenon that a significant reduction in thermal expansion rate can be obtained (see Fig. 1-1). Furthermore, the inventors paid attention to the fact that by blending fine cellulose powder, a small amount of blending can obtain a sufficient effect of reducing the thermal expansion coefficient. After careful investigation, they found that blending is used to ensure toughness, etc. Fillers such as silicon dioxide with various characteristics required for the insulating materials of electronic parts can be mixed with the fine cellulose powder at the same time to obtain the above-mentioned unique effects of the present invention (see FIGS. 1-2 and 1-3).

As the fine powder described above, when a hydrophilic fine powder is used, it is preferable to subject the particles to a hydrophobic treatment or to a surface treatment using a coupling agent. Such a treatment can be performed by a known and customary method suitable for fine powder.

The blending amount of the fine powder in the present invention is more preferably 0.04 to 64% by mass, more preferably 0.08 to 30% by mass, and more preferably 0.1 to 10% by mass relative to the total amount of the composition for removing the solvent. . When the blending amount of the fine powder is 0.04 mass% or more, a good effect of reducing the linear expansion coefficient or a good effect of improving the adhesion with the plated copper can be obtained. On the other hand, when it is 64% by mass or less, the film forming property is improved.

Among the fine powders related to the present invention, the fine cellulose powder can be obtained from the following, but is not limited to these.

(Fine cellulose powder) As a raw material of the fine cellulose powder, wood or natural plant fiber materials obtained from hemp, bamboo, cotton, jute, kenaf, flax bales, agricultural waste, and cloth can be used. Among the regenerated cellulose fibers, such as pulp, water chestnut, or cellulan, especially, pulp is more suitable. As the pulp, chemical pulp, semi-chemical pulp, and chemically ground wood pulp such as kraft pulp, sulfite pulp, and the like obtained by chemically or mechanically using plant raw materials can be used. Mud, chemical mechanical pulp mud, thermomechanical mud mud, chemical thermomechanical mud mud, refined grinding mud, wood pulp mud, and deinked old pulp mud, magazine old pulp mud, carton with these plant fibers as the main component Old pulp and mud. Among them, various types of kraft pulp from coniferous trees with strong fiber strength, such as unbleached kraft pulp from coniferous trees, unbleached kraft pulp from coniferous acids, and bleached kraft pulp from coniferous trees are particularly suitable.

The above raw materials are mainly composed of cellulose, hemicellulose, and wood, and the content of wood is usually about 0 to 40% by mass, especially about 0 to 10% by mass. With regard to these raw materials, it is possible to perform wood removal or bleaching, or to adjust the quality of wood, if necessary. The measurement of the wood content can be performed by the Klason method.

In the cell wall of plants, cellulose molecules are not single molecules, but form crystalline microfibers (fine cellulose fibers) that regularly aggregate and aggregate dozens of them, which is the basic skeleton substance of plants. Therefore, in order to produce fine cellulose powder from the above-mentioned raw materials, fibers are oxidized by applying a non-beating pulverization treatment, high-temperature and high-pressure steam treatment, phosphate treatment, and the like, using N-oxygen compounds as oxidation catalysts. For the treatment of plain fibers, a method of unbundling the fibers into a nano size can be used.

In the above, the non-beating pulverization process is a method of disintegrating fibers by applying direct force to raw materials such as the above-mentioned sludge and performing pulverization without mechanical knock to obtain fine cellulose powder. More specifically, for example, a cellulose suspension having a fiber diameter of about 0.1 to 10 μm can be made into a water suspension of about 0.1 to 3% by mass by mechanically treating a slurry or the like with a high-pressure homogenizer. Further, this is repeatedly pulverized without grinding by a grinder or the like to obtain a fine cellulose powder having a fiber diameter of about 10 to 100 nm.

The non-grinding and pulverizing treatment can be performed using, for example, a "Pure Fine Mill" manufactured by Kurita Machinery Co., Ltd. or the like. This grinder is a stone mortar grinder that grinds raw materials to ultrafine particles by using the punching force, centrifugal force, and shearing force generated when the raw materials pass through the gap between the two upper and lower grinders, and can simultaneously cut and grind. , Micronization, dispersion, emulsification and fibrosis. In addition, the above-mentioned non-grinding pulverizing process can be performed using a super fine particle grinder "Super Masscolloider" made by Masuko Industries. Super Masscolloider is a grinder that can be ultra-micronized beyond the simple crushing area and feels like it is melting. Super Masscolloider is an ultrafine particle grinder in the form of a stone mortar that can be adjusted freely and consists of two non-porous grinding stones. The upper grinding stone is fixed and the lower grinding stone will rotate at high speed. The raw materials put into the feed tank will be sent into the gap between the upper and lower millstones due to the centrifugal force. Due to the strong compression, shearing and rotational friction generated by this, the raw materials will be ground in order and ultra-micronized.

In addition, the high-temperature and high-pressure water vapor treatment is a method of obtaining fine cellulose powder by exposing the raw materials such as the slurry to high-temperature and high-pressure water vapor and disentangling the fibers.

Furthermore, the treatment of the above-mentioned phosphate is to reduce the bonding force between the cellulose fibers by performing phosphate esterification on the surface of the raw materials such as the slurry, and then to dissolve the fibers by a purification machine treatment to obtain fine fibers. Treatment method of plain powder. For example, the raw materials such as the above sludge are immersed in a solution containing 50% by mass of urea and 32% by mass of phosphoric acid, the solution is sufficiently sucked between cellulose fibers at 60 ° C, and then phosphorylated by heating at 180 ° C. After this water washing, it was hydrolyzed in a 3% by mass aqueous hydrochloric acid solution at 60 ° C for 2 hours, and then washed again. Then, it was phosphorylated in a 3% by mass aqueous sodium carbonate solution for about 20 minutes at room temperature. After completion, the treated product is defibrated with a purifier to obtain fine cellulose powder.

In addition, the treatment of oxidizing cellulose fibers using the N-oxygen compound as an oxidation catalyst is a method of oxidizing raw materials such as the above-mentioned sludge, and then obtaining a fine cellulose powder by miniaturization.

First, the natural cellulose fibers are dispersed in water having an absolute dry basis of about 10 to 1,000 times (mass basis), and dispersed using a mixer or the like to prepare an aqueous dispersion. As the natural cellulose fiber used as a raw material of the above-mentioned fine cellulose fibers, for example, wood pulp such as coniferous pulp or broadleaf pulp, non-wood pulp such as wheat straw pulp or bagasse pulp, cottonseed wool, or Cotton pulp such as cotton linter, bacterial cellulose, etc. These can be used singly or in combination of two or more kinds as appropriate. In addition, in order to increase the surface area in advance, such natural cellulose fibers may be subjected to a treatment such as beating.

Next, in the aqueous dispersion, an N-oxygen compound was used as an oxidation catalyst, and an oxidation treatment of natural cellulose fibers was performed. As related N-oxygen compounds, for example, in addition to TEMPO (2,2,6,6-tetramethylpiperidine-N-oxy), 4-carboxy-TEMPO, 4-acetamido-TEMPO, 4 -Amine-TEMPO, 4-dimethylamino-TEMPO, 4-phosphinofluorenyloxy-TEMPO, 4-hydroxyTEMPO, 4-oxyTEMPO, 4-methoxyTEMPO, 4- (2-bromo Acetylamino) -TEMPO, 2-azaadamantane N-oxygen, etc. are TEMPO derivatives having various functional groups at the C4 position. The amount of these N-oxygen compounds to be added is sufficient as the amount of the catalyst, and can usually be set within a range of 0.1 to 10% by mass based on the absolute drying basis with respect to natural cellulose fibers.

In the oxidation treatment of the above-mentioned natural cellulose fibers, an oxidant and a co-oxidant are used together. Examples of the oxidizing agent include halogenous acid, hypohalous acid and perhalic acid, and salts thereof, hydrogen peroxide, and perorganic acid. Among them, alkali metals such as sodium hypochlorite and sodium hypobromite are mentioned. Hypohalites are more suitable. In addition, as the co-oxidant, an alkali bromide metal such as sodium bromide can be used. The amount of the oxidant can usually be set within the range of about 1 to 100% by mass based on the absolute drying standard, and the amount of the co-oxidant can be set on the absolute dry basis relative to the natural cellulose fiber. The range is about 1 to 30% by mass.

During the above-mentioned natural cellulose fiber oxidation treatment, it is preferable to maintain the pH of the aqueous dispersion in the range of 9 to 12, and to proceed the oxidation reaction efficiently. In addition, the temperature of the aqueous dispersion during the oxidation treatment can be arbitrarily set within a range of 1 to 50 ° C, and the reaction can be performed at room temperature without temperature control. The reaction time can be set in a range of 1 to 240 minutes. In addition, a penetrant may be added to the aqueous dispersion to penetrate the inside of the natural cellulose fiber and introduce more carboxyl groups into the fiber surface. Examples of the penetrant include anionic surfactants such as carboxylates, sulfates, sulfonates, and phosphates; or nonionic surfactants such as polyethylene glycols and polyols.

After the above-mentioned natural cellulose fiber is subjected to an oxidation treatment and before being refined, a purification treatment for removing impurities such as unreacted oxidizing agents and various by-products contained in the aqueous dispersion is preferred. Specifically, methods such as washing with natural cellulose fibers subjected to oxidation treatment and repeated filtration can be used. The natural cellulose fibers obtained after the purification treatment can usually be supplied to the miniaturization treatment in a state of being impregnated with an appropriate amount of water. However, if necessary, they can be dried to become fibrous or powdery.

Next, the miniaturization of the natural cellulose treatment is carried out in a state where the purified natural cellulose fibers are dispersed in a solvent such as water, as desired. As a dispersing medium used in the miniaturization process, water is generally preferred, but alcohols (methanol, ethanol, isopropanol, isobutanol, sec-butanol, tert-butanol, Methylcellulose, ethylcellulose, ethylene glycol, glycerol, etc.) or ethers (ethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, etc.), ketones (acetone, formazan Methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylmethane, etc.) can be used in water-soluble organic solvents, and these mixtures can also be used .固 The solid content concentration of the natural cellulose fibers in the dispersion of these solvents is more preferably 50% by mass or less. If the solid content concentration of the natural cellulose fiber exceeds 50% by mass, extremely high energy is required in dispersion, so it is not preferable. The refinement of natural cellulose processing can use low-pressure homogenizers, high-pressure homogenizers, grinders, coarse grinders, ball mills, jet mills, beaters, dissociators, short-axis extruder, 2-axis extruder, ultrasonic This is performed by a dispersing device such as a blender, a domestic juicer, and the like.

The fine cellulose powder obtained by the miniaturization treatment can be adjusted to have a solid content concentration in the form of a suspension or dried to a powder form as desired. Here, when it is in the form of a suspension liquid, only water can be used as a dispersing medium, and water and other organic solvents such as alcohols such as ethanol or a mixed solvent with a surfactant, an acid, or a base can also be used.

Through the above-mentioned oxidation treatment and miniaturization treatment of the natural cellulose fiber, the hydroxyl group at the C6 position of the cellulose molecular constituent unit is selectively oxidized to a carboxyl group through an aldehyde group, and a related carboxyl group content of 0.1 to 3 mmol / g can be obtained. A highly crystalline fine cellulose powder having cellulose molecules of the above specific number average fiber diameter. This highly crystalline fine cellulose powder has a cellulose type I crystal structure. This means that the relevant fine cellulose powder is a cellulose molecule derived from natural molecules having a type I crystal structure that has undergone surface oxidation and has been refined. That is, natural cellulose fibers are produced during the process of biosynthesis, and the fine fibers called microfibers are formed into a high-order solid structure after multi-bundling. They are introduced by oxidized aldehyde groups or carboxyl groups. The strong cohesive force (hydrogen bonding between the surfaces) between the microfibers is weakened, and further, a fine cellulose powder is obtained by the miniaturization treatment. By adjusting the oxidation treatment conditions, the content of carboxyl groups can be increased or decreased, the polarity can be changed, or the electrostatic reversion or miniaturization treatment of carboxyl groups can be used to control the average fiber diameter or average fiber length and average length of fine cellulose powder. Aspect ratio, etc.

The above-mentioned natural cellulose fiber has an I-type crystal structure, and has a diffraction pattern obtained by measuring a wide-angle X-ray diffraction image thereof at two positions near 2θ = 14 to 17˚ and 2θ = 22 to 23 像. Typical wave crests are identified. In addition, the introduction of carboxyl groups into the cellulose molecules of the fine cellulose powder enables the presence of carbonyl groups in the total reflection infrared spectroscopy (ATR) in the sample in which moisture is completely removed (near 1608cm ^-1 ). To confirm. When it is a carboxyl group (COOH), there is absorption at 1,730 cm ^{-1 in the} above measurement.

In addition, the natural cellulose fibers after the oxidation treatment may have halogen atoms attached or bonded, and a halogen removal treatment may be performed for the purpose of removing such residual halogen atoms. The dehalogenation treatment is performed by immersing the natural cellulose fibers after the oxidation treatment 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, with a bath ratio of about 1: 5 to 1: 100, preferably 1:10 to 1: It is impregnated under conditions of about 60 (mass ratio). At this time, the concentration of the hydrogen oxide solution is more preferably 1 to 50 g / L, and more preferably 5 to 20 g / L. Moreover, the pH value of the hydrogen peroxide solution is more preferably 8 to 11, and more preferably 9.5 to 10.7.

In addition, the amount of the carboxyl group [mmol / g] in cellulose relative to the mass of the fine cellulose powder contained in the aqueous dispersion can be evaluated by the following method. That is, a 0.5 to 1% by mass aqueous dispersion of a fine cellulose powder sample after weighing and drying in 60 ml is prepared in advance, and the pH value is set to about 2.5 with a 0.1 M hydrochloric acid aqueous solution, and then 0.05 M of hydroxide is dropped. The sodium conductivity was measured until the pH reached about 11. The amount of functional groups can be determined from the amount of sodium hydroxide (V) consumed in the neutralization stage of a weak acid whose electrical conductivity changes slowly. The amount of the functional group indicates the amount of the carboxyl group. Functional group amount [mmol / g] = V [ml] × 0.05 / fine cellulose powder sample [g]

In addition, the fine cellulose powder used in the present invention may be chemically modified and / or physically modified to improve its functionality. Here, as the chemical modification, functional groups can be added by acetalization, acetylation, cyanoethylation, etherification, isocyanation, or the like, or inorganic substances such as silicate or titanate can be added by A chemical reaction, a sol-gel method, or the like is used to composite them or to coat them. As a method for chemical modification, for example, a method in which a fine cellulose powder formed into a sheet shape is immersed in acetic anhydride and then heated is used. In addition, the fine cellulose powder obtained by the treatment of oxidizing cellulose fibers with N-oxygen compounds as oxidation catalysts includes amine compounds or quaternary modified amine compounds by ionic bonding or amidine bonding to carboxyl groups in the molecule. Methods of ammonium compounds and the like. Examples of physical modification include physical vapor deposition (PVD method), chemical vapor deposition (CVD method), electroless plating, or electrolysis of a metal or ceramic material by vacuum evaporation, ion plating, sputtering, or the like. A coating method such as a plating method such as plating. These modifications can also be made before or after the treatment.

When the fine cellulose powder used in the present invention is fibrous, it is desirable that its average fiber diameter is 3 nm or more and smaller than 100 nm. Since the minimum diameter of the fine cellulose fiber single fiber is 3 nm, it cannot be produced substantially when it is less than 3 nm. In addition, if it is smaller than 100 nm, it is not necessary to add excessively, and the desired effect of the present invention can be obtained, and the film forming property is also good. The average fiber diameter of the fine cellulose powder can be measured by the method for measuring the size of the fine powder.

(Cellulose Nanocrystalline Particles) The present inventors have paid more attention to the crystalline morphology of fine cellulose powder and have conducted intensive investigations to find that the cellulose raw material is hydrolyzed to remove the non-crystalline portion, and only the crystalline portion is separated. Supra-nanocrystalline particles can unexpectedly solve the above-mentioned problems, and provide a curable resin composition having an excellent life span. As a filler, the use of cellulose nanocrystal particles separated from the crystalline portion of cellulose raw materials and fillers other than the cellulose nanocrystal particles in combination can provide a hardenable resin composition having an excellent life span. It is possible to obtain a hardened product which can maintain a low thermal expansion coefficient in a temperature region when a component exceeding 200 ° C is installed, and has various properties such as toughness and heat resistance.

Furthermore, the inventors focused on cellulose nanocrystalline particles separated only from the crystalline portion of the cellulose raw material, and compared the relationship between the blending amount and the thermal expansion coefficient with silicon dioxide and studied meticulously. Even a small amount of the elementary nanocrystalline particles can obtain a significant thermal expansion coefficient reduction effect (see FIG. 6-1). In addition, the inventors have found that by blending fillers such as silicon dioxide with various characteristics required for insulating materials such as toughness and heat resistance of electronic parts, and simultaneously using and mixing the cellulose nanocrystal particles, the above-mentioned can be obtained. The unique effect of the present invention (see Figs. 6-2, 6-3). Furthermore, the inventors have been able to provide a hardenable resin composition with an excellent service life by using cellulose nanocrystalline particles composed of only crystalline portions, which is not possible with fine cellulose powder containing non-crystalline portions. Special effects.

In the present invention, cellulose nanocrystalline particles mean that as long as the cellulose raw material is hydrolyzed with a high concentration of mineral acid (hydrochloric acid, sulfuric acid, hydrobromic acid, etc.) to remove the non-crystalline portion and only the crystalline portion is separated, it can be used. Either particle. As the size of the particles, an average crystal width of 3 to 70 nm and an average crystal length of 100 to 500 nm are preferable, and an average crystal width of 3 to 50 nm is more preferable, and an average crystal length of 100 to 400 nm is more preferable. Preferably, the average crystal width is 3 to 10 nm, and the average crystal length is 100 to 300 nm. Here, the crystalline width means the short side length of the particles, and the crystalline length means the long side length of the particles. Such cellulose nanocrystalline particles have a larger surface area per unit mass and a larger proportion of atoms exposed on the surface than a width or length larger than this. Therefore, it is thought that the cellulose nanocrystalline particles will achieve the mutual effect of pulling each other, and exhibit the reinforcing effect, and the thermal expansion property will be reduced.

Here, the size (average crystal width, average crystal length) of cellulose nanocrystal particles can be measured by SEM (Scanning Electron Microscope; Scanning Electron Microscope), TEM (Transmission Electron Microscope; Transmission Electron Microscope), or AFM (Atomic Force) Microscope; atomic force microscope). Specifically, in the diagonal drawing of the microscope picture, 12 points in the vicinity of the particle are randomly selected and the size can be measured. After removing the largest particle and the smallest particle, the size of the remaining 10 points (crystal width, Crystal length), and the averaged values are the average crystal width and average crystal length of the cellulose nanocrystal particles, respectively.

As the cellulose nanocrystal particles, two or more different kinds of raw material cellulose may be used in combination.

It is preferable to apply such cellulose nanocrystal particles to a surface treatment using hydration treatment, a coupling agent, and the like. Such a treatment can be performed by a known conventional method suitable for cellulose nanocrystal particles.

The blending amount of the cellulose nanocrystalline particles in the present invention is more preferably 0.04 to 30% by mass, more preferably 0.08 to 20% by mass, and more preferably 0.1 to the total amount of the solvent-removing composition. 10% by mass. When the blending amount of the cellulose nanocrystal particles is 0.04% by mass or more, the effect of reducing the thermal expansion coefficient can be obtained satisfactorily. On the other hand, when it is 30% by mass or less, the film forming property is improved.

The cellulose nanocrystal particles related to the present invention can be obtained by hydrolyzing a cellulose raw material with a high concentration of mineral acids (hydrochloric acid, sulfuric acid, hydrobromic acid, etc.) to remove the non-crystalline portion and separating only the crystalline portion. Here, as the cellulose raw material, there are pulp pulp for making paper, cotton pulp such as cotton linters or cotton fluff, non-wood pulp such as hemp, wheat straw, bagasse, etc., which are separated from ascidians or seagrasses. The cellulose and the like are not particularly limited. Among these, cotton or sea squirt is preferable from the viewpoint of obtaining ease, from the viewpoint of making pulp for paper making, and from the viewpoint of being able to produce CNC with more excellent heat resistance. Examples of the pulp for papermaking include broadleaf kraft pulp and coniferous kraft pulp. Examples of the broadleaf kraft pulp include tanned kraft pulp (LBKP), untanned kraft pulp (LUKP), and oxygen-bleached kraft pulp (LOKP). Examples of the coniferous kraft pulp include tanned kraft pulp (NBKP), untreated kraft pulp (NUKP), and oxygen-bleached kraft pulp (NOKP). In addition, there are chemical slurry, semi-chemical slurry, mechanical slurry, non-wood slurry, and deinked slurry using old paper as a raw material. Examples of the chemical slurry include sulfite slurry (SP) and caustic soda slurry (AP). As semi-chemical pulps, there are semi-chemical pulps (SCP) and chemically ground wood pulps (CGP). Examples of mechanical pulp include ground wood pulp (GP), thermomechanical pulp (TMP, BCTMP), and the like. As non-wood pulp, there are those who use tadpoles, sassafras, hemp, kenaf, etc. as raw materials. This kind of cellulose raw material can also be used alone, and the liquid can be used in combination of two or more. In addition, cellulose nanofibers (hereinafter simply referred to as "CNF") produced by a mechanical defibration method, a phosphate method, a TEMPO oxidation method, or the like may be used as a cellulose raw material.

Next, as described above, the hydrolysis of the cellulose raw material can be performed, for example, by treating the aqueous suspension or slurry containing the cellulose raw material with sulfuric acid, hydrochloric acid, hydrobromic acid, or the like, or by directly suspending the cellulose raw material in sulfuric acid, hydrochloric acid, It is performed in an aqueous solution such as hydrobromic acid. In particular, when slurry is used as a cellulose raw material, it is preferable to use a coarse grinder, a pin mill, or the like to form a cotton-like fiber, and then subject it to a hydrolysis treatment, so that a uniform hydrolysis treatment can be performed. In such a hydrolysis treatment, the temperature conditions are not particularly limited, but can be set to, for example, 25 to 90 ° C. The conditions of the hydrolysis treatment time are not particularly limited, but can be set to, for example, 10 to 120 minutes. In addition, the cellulose nanocrystal particles obtained by hydrolyzing the cellulose raw material in this way can be subjected to a neutralization treatment using, for example, a base such as sodium hydroxide.

The cellulose nanocrystal particles thus obtained can be micronized as necessary. In this micronization process, a processing apparatus or a processing method is not specifically limited. As the micronization treatment device, for example, a grinder (stone mortar type pulverizer) or a high-pressure homogenizer, an ultra-high-pressure homogenizer, a high-pressure conflict-type pulverizer, a ball mill, a bead mill, a table-type purification machine, and a conical purification machine can be used. , Two-shaft kneading machine, vibration mill, homomixer rotating at high speed, ultrasonic disperser, beater, etc.

In the micronization treatment, it is preferable to dilute the cellulose nanocrystal particles into a slurry form by using water or an organic solvent alone or in combination, but it is not particularly limited. Examples of preferred organic solvents include alcohols, ketones, ethers, dimethylsulfinium (DMSO), dimethylformamide (DMF), and dimethylacetamide (DMAc). The dispersion medium may be one kind, or two or more kinds. The dispersion medium may contain solid components other than cellulose nanocrystal particles, such as urea having hydrogen bonding properties.

In addition, the cellulose nanocrystal particles used in the present invention may be chemically modified and / or physically modified to improve the functionality. Here, as the chemical modification, functional groups can be added by acetalization, acetylation, cyanoethylation, etherification, isocyanation, or the like, or inorganic substances such as silicate or titanate can be added by A chemical reaction, a sol-gel method, or the like is used to composite them or to coat them. The physical modification can be performed by plating or evaporation.

[Fillers other than fine powder] 树脂 The resin composition of the present invention further contains fillers other than the above fine powder. Examples of such fillers include barium sulfate, barium titanate, amorphous silica, crystalline silica, molten silica, spherical silica, talc, white clay, magnesium carbonate, calcium carbonate, and aluminum oxide. , Aluminum hydroxide, silicon nitride, aluminum nitride, titanium oxide and other inorganic fillers. In addition, when the fine powder is cellulose nanocrystalline particles, it may also be an organic filler, and cellulose nanofibers may also be used as an organic filler. Among the fillers, silicon dioxide is preferred.填料 The average particle diameter of this filler is preferably 3 μm or less, and even more preferably 1 μm or less. The average particle diameter of the filler can be determined by a laser diffraction type particle diameter distribution measuring device.

The blending amount of this filler is 1 to 90% by mass, preferably 2 to 80% by mass, and still more preferably 5 to 75% by mass in the total amount of the composition excluding the solvent. By setting the blending amount of the filler within the above range, the coating film performance of the hardened product after hardening can be well ensured.

The blending ratio of fillers other than fine powder and fine powder in the whole filler is based on mass ratio (filler other than fine powder: fine powder) = 100: (0.04 ~ 30), preferably 100: (0.1 ~ 20), and more preferably 100: (0.2 ~ 10). By using the filler in such a blending ratio, it is possible to maintain a low thermal expansion rate, and at the same time, to achieve various contradictions such as toughness and heat resistance required for the insulating material of electronic parts. In addition, the total amount of fillers blended in the curable resin composition is preferably a known amount appropriately used in accordance with the characteristics required for the use of the curable resin composition, such as insulating materials such as interlayer insulating materials for electronic parts. .

<Removal of the fine powders of the first and sixth objects and other blending ingredients other than the fillers of the fine powders> 中 In the first aspect of the present invention, the first and sixth objects of the fine powders and fines are removed The other blending ingredients of the filler other than the powder are as follows.

[Curable resin] 树脂 In the present invention, the curable resin is not particularly limited, and a known one can be used. For example, it may be a material containing any one of a thermosetting component and a photocurable component, but it includes a thermosetting material. The material of the sexual component is preferred. As the thermosetting component, any resin that exhibits electrical insulation properties by heat curing may be used. For example, a compound having a cyclic ether group such as an epoxy compound or a propylene oxide compound, a melamine resin, a siloxane resin, and benzene can be used. Amine resins such as guanamine resins, melamine derivatives, benzoguanamine derivatives, polyisocyanate compounds, block isocyanate compounds, cyclic carbonate compounds, episulfide resins, bismaleimide, and carbodiimide Well-known thermosetting resins, such as resin, polyimide resin, polyimide resin, polyphenylene ether resin, and polyphenylene sulfide resin. In particular, a thermosetting resin having at least any one of a cyclic ether group and a cyclic thioether group (hereinafter abbreviated to a cyclic (thio) ether group) in the molecule is preferred. Among these, epoxy compounds and propylene oxide compounds are preferred, and epoxy resins of epoxy compounds are even more preferred.

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, bisphenol M epoxy resin, and bisphenol. P-type epoxy resin, bisphenol Z-type epoxy resin, bisphenol-type epoxy resin, bisphenol A varnish-type epoxy resin, novolac-type epoxy resin, cresol varnish-type epoxy resin, and other varnish-type epoxy resin Resin, biphenyl epoxy resin, biphenylarane epoxy resin, aryl extended alkylene epoxy resin, tetrahydroxyphenylethane epoxy resin, naphthalene epoxy resin, onion epoxy resin, benzene Oxygen-type epoxy resin, dicyclopentadiene-type epoxy resin, original norbornene-type epoxy resin, adamantane-type epoxy resin, fluorene-type epoxy resin, glycidyl methacrylate copolymer epoxy resin, Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, epoxy modified polybutadiene rubber derivative, CTBN modified epoxy resin, trimethylolpropane glycidyl ether, Phenyl-1,3-diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethyl Of alcohol or propylene glycol diglycidyl ether, sorbitol glycidyl ether, ginseng (2,3-epoxy propyl) isocyanurate, triglycidyl tris (2- hydroxyethyl) isocyanate, a phenoxy resin and the like. Among them, it is used for at least one of a solid epoxy resin having a solid shape at 40 ° C and a semi-solid epoxy resin having a solid shape at 20 ° C and a liquid shape at 40 ° C, and a liquid at 20 ° C. It is preferable to use a liquid epoxy resin in the form of a liquid in order to maintain the effect of the present invention, and at the same time have more excellent crack resistance during cold and hot cycles. Examples of solid epoxy resins, semi-solid epoxy resins, and liquid epoxy resins are described in Japanese Patent Application Laid-Open No. 2015-10232.

The said thermosetting component can be used together with a hardening agent as needed. Examples of the hardening agent include phenol resins, polycarboxylic acids and their anhydrides, cyanate resins, active ester resins in which hydroxyl groups are blocked by ethylation, etc., and cyclic olefin polymers having a carboxyl group or a hydroxyl group in a side chain and an active ester structure. Or a curing agent having a substituent capable of reacting with a cyclic ether group having a hydroxyl group, a carboxyl group, and an active ester structure as part of the curable resin, can be used alone or in combination of two or more kinds.

As the phenol resin, a phenol novolak resin, an alkyl novolak resin, a bisphenol A varnish resin, a dicyclopentadiene type phenol resin, a Xylok type phenol resin, a terpene modified phenol resin, and a cresol / naphthol resin can be used. , Polyvinyl phenols, phenol / naphthol resin, α-naphthol skeleton-containing phenol resin, and triazine-containing cresol varnish resin.

The above polycarboxylic acids and their anhydrides are compounds having two or more carboxyl groups in one molecule and their anhydrides, and examples thereof include copolymers of (meth) acrylic acid, copolymers of maleic anhydride, and condensates of dibasic acids. Other resins having a carboxylic acid terminal, such as a carboxylic acid terminal and an imine resin.

The cyanate resin is a compound having two or more cyanate groups (-OCN) in one molecule. As the cyanate resin, any of conventionally known ones can be used. Examples of the cyanate resin include novolac cyanate resin, alkyl novolac cyanate resin, dicyclopentadiene cyanate resin, bisphenol A cyanate resin, and bisphenol F. Type cyanate resin, bisphenol S type cyanate resin. Also, it may be a part of the tri-polymerized prepolymer.

The above-mentioned active ester resin is not particularly limited, but is preferably a resin having two or more active ester groups in one molecule. The active ester resin can be generally obtained by a condensation reaction of one or more of a carboxylic acid compound and a thiocarboxylic acid compound with one or more of a hydroxy compound and a thiol compound. Examples of the active ester resin include dicyclopentadienyl diphenol ester compounds, bisphenol A diacetate, diphenyl phthalate, diphenyl terephthalate, and bis [4- (terephthalate) Methoxycarbonyl) phenyl] and the like. In addition, the active ester resin is suitable for obtaining electronic parts that have a low relative permittivity and a low loss factor and have low dielectric properties.

Such a thermosetting component or a hardening agent can be blended with a known composition suitable for use in accordance with the use of the thermosetting resin composition as a constituent component, such as characteristics required for insulating materials such as interlayer insulating materials for electronic parts. Mix better.

In the present invention, as the thermosetting resin composition containing the above-mentioned thermosetting component, in addition to the above components, a polymer resin such as a thermoplastic resin, an elastomer, a rubber-like particle, an imidazole compound or an amine compound, Hardening accelerators for ammonia compounds, phosphorus compounds, S-triazine derivatives, diluents for flame retardants, colorants, organic solvents, and other additives.

Next, as the photocurable component, any resin that exhibits electrical insulation properties by curing with light irradiation may be used. Examples thereof include alkanes such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate. (Meth) acrylates; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc .; ethylene glycol, propylene glycol Mono- or di (meth) acrylates of alkylene oxide derivatives, such as diethylene glycol, diethylene glycol, dipropylene glycol; hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, di Polyols such as pentaerythritol, parahydroxyethyl isocyanate, or poly (meth) acrylates of these ethylene oxide or propylene oxide adducts; poly (phenoxyethyl) (meth) acrylate, bisphenol A Ethoxy di (meth) acrylate and other phenolic ethylene oxide or propylene oxide adduct (meth) acrylates; glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl Glyceryl isocyanate and other glycidyl ether (meth) acrylates; and melamine Amine (meth) acrylate and the like.

The said photocurable component can be used together with the photoreaction initiator which produces | generates any one of a radical, a salt group, and an acid as needed. Examples of the photoreaction initiator include bis- (2,6-dichlorobenzyl) phenylphosphine oxide and bis- (2,6-dichlorobenzyl) -2,5-dimethyl. Phenylphenylphosphine oxide, bis- (2,6-dichlorobenzyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzyl) -1-naphthyl oxide Phosphine, bis- (2,6-dimethoxybenzyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzyl) -2,4,4-trimethyl n- Amylphosphine oxide, bis- (2,6-dimethoxybenzyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzyl) ) -Phenylphosphine oxides (made by BASF JAPAN (stock), IRGACURE819) and other bisfluorenylphosphine oxides; 2,6-dimethoxybenzyldiphenylphosphine oxide, 2,6-dichlorobenzene Formamyldiphenylphosphine oxide, 2,4,6-trimethylbenzylphenylphenylphosphite methyl ester, 2-methylbenzyldiphenylphosphine oxide, trimethylacetamyl Monofluorenylphosphine oxides such as isopropyl phenyl hypophosphite, 2,4,6-trimethylbenzylidene diphenylphosphine oxide (BASF JAPAN (shares), DAROCUR TPO); 1-hydroxyl -Cyclohexylphenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2 -Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propanyl) -benzyl] phenyl} -2-methyl-propane-1-one, 2-hydroxy-2- Hydroxyacetophenones such as methyl-1-phenylpropane-1-one; benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n- Butyl ether and other benzoin; benzoin alkyl ethers; diphenyl ketone, p-methyl diphenyl ketone, Michler's Ketone, methyl diphenyl ketone, 4,4'-dichloro Diphenyl ketones such as diphenyl ketone, 4,4'-bisdiethylaminodiphenyl ketone; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio ) Phenyl] -2-morpholinyl-1-acetone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1, N, N-di Acetophenones such as methylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4- Diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and other thioxanthone; Scallion shallots, 2-ethyl shallot shallot, 2-tert-butyl shallot shallot, 1-chloro shallot shallot, 2-pentyl shallot shallot, 2-amino shallot shallot, etc .; acetophenone dimethyl Ketals, ketals of benzyl dimethyl ketal, etc .; ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate, p-di Benzoic acid esters such as ethyl methyl benzoate; 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzylidene oxime)], ethyl ketone, 1- [9-Ethyl-6- (2-methylbenzylidene) -9H-azolecarb-3-yl]-, 1- (0-acetamidooxime) and other oxime esters; bis ( η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium, bis (cyclopentadienyl)- Bis [2,6-difluoro-3- (2- (1-pyrrole-1-yl) ethyl) phenyl] titanium, etc .; titanium disulfide; Anisyl ethyl ether, azobisisobutyronitrile, tetramethyl disulfide thiuram, etc. The above photoreaction initiators may be used singly or in combination of two or more.

Such a photocurable component or a photoreaction initiator can be used as a constituent of a photocurable resin composition, for example, characteristics required for an insulating material such as an interlayer insulating material of an electronic component, etc., to suit a conventionally known composition It is better to blend.

In the present invention, the photocurable resin composition containing the photocurable component may include, in addition to the above components, a polymer resin such as a thermoplastic resin, an elastomer, and rubber-like particles, a sensitizer, and a flame retardant. , Colorants, thinners for organic solvents, and other additives.

In addition, when the curable resin composition of the present invention is used as an alkali-developed photo-solder photoresist composition capable of developing with an alkali aqueous solution, a carboxyl group is used in addition to the above-mentioned thermo-hardening component and photo-hardening component. The resin is preferred.

(Carboxyl-containing resin) As the carboxyl-containing resin, a photosensitive carboxyl-containing resin having one or more photosensitive unsaturated double double bonds and a carboxyl-containing resin having no photosensitive unsaturated double bond can be used. Either is not limited to a special one. As the carboxyl group-containing resin, in particular, the resins listed below can be suitably used. (1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and a compound having an unsaturated double bond, and a carboxyl group-containing resin whose molecular weight or acid value is modified by modifying it. (2) A photosensitive carboxyl group-containing resin obtained by reacting a carboxyl group-containing (meth) acrylic copolymer resin with a compound having an ethylene oxide ring and an ethylenically unsaturated group in one molecule. (3) A copolymer of a compound having an epoxy group and an unsaturated double bond and a compound having an unsaturated double bond, respectively, in one molecule is reacted with an unsaturated monocarboxylic acid, so that the second order produced by the reaction A photosensitive carboxyl group resin obtained by reacting a hydroxyl group with a saturated or unsaturated polybasic acid anhydride. (4) Photosensitivity obtained by reacting a hydroxyl-containing polymer with a saturated or unsaturated polybasic acid anhydride, and reacting a carboxylic acid formed by the reaction with a compound having one epoxy group and an unsaturated double bond in each molecule. Resin containing hydroxyl and carboxyl groups. (5) A photosensitive carboxyl group-containing resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting a part or all of the second-stage hydroxyl group formed by the reaction with a polybasic acid anhydride. (6) A polyfunctional epoxy compound is reacted with a compound having one reactive group other than a hydroxyl group having two or more hydroxyl groups and epoxy groups in one molecule, reacted with an unsaturated monocarboxylic acid, and then Carboxyl-containing photosensitive resin obtained by reacting the obtained reaction product with a polybasic acid anhydride. (7) The reaction product obtained by reacting a resin having a phenolic hydroxyl group with an alkylene oxide or a cyclic carbonate with an unsaturated monocarboxylic acid, and then reacting the obtained reaction product with a polybasic acid anhydride Carboxyl photosensitive resin. (8) A polyfunctional epoxy compound is reacted with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule with an unsaturated monocarboxylic acid, and then the alcohol of the obtained reaction product is reacted. A carboxyl group-containing photosensitive resin obtained by reacting a hydroxyl group with an anhydride group of a polybasic acid anhydride.

This carboxyl group-containing resin is preferably blended with a known composition commonly used in alkali-developing curable resin compositions such as solder photoresist compositions containing the resin as a constituent.

As described above, in the curable resin composition of the present invention, it is possible to further appropriately mix other conventionally used blending components in accordance with its use. Examples of other commonly used blending ingredients include polymer resins such as the aforementioned thermoplastic resins, elastomers, and rubber-like particles, hardening accelerators, sensitizers, flame retardants, colorants, and organic solvents. Diluents and other additives are specifically known and commonly used additives such as a defoamer, a leveler, a shake-miscibility imparting agent, a thickener, a coupling agent, and a dispersant.

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

Red colorants: As red colorants, monoazo-based, diazo-based, azo lake-based, benzimidazolone-based, fluorene-based, diketopyrrolopyrrole-based, condensed azo-based, ANT- 35 scallions, quinacridone, etc.

Blue colorant, green colorant: As a blue colorant or green colorant, there are titanium cyanine-based, scallion-onion-based, and pigment-based compounds classified as pigments. Specific examples include Number of colored index (CI; issued by The Society of Dyers and Colourists). In addition, metal substituted or unsubstituted titanium cyanine compounds can also be used.

Yellow colorants: As yellow colorants, monoazo-based, diazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, and shallot-based shall be mentioned.

In addition, for the purpose of adjusting hue, colorants such as purple, orange, brown, and black may be added.

The specific blending ratio of the colorant can be appropriately adjusted depending on the type of the colorant used or other types of additives.

Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cyrus, ethyl cyrus, butane Kiselosulfone, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, etc. Alcohol ethers; Ethyl acetate, butyl acetate, celex acetate, diethylene glycol monoethyl ether acetate, and esters of the above-mentioned glycol ethers; ethanol, propanol, ethyl Alcohols such as diols and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and solvent oil.

The curable resin composition of the present invention containing the components described above may be used after being dried into a film, or may be used directly as a liquid. In addition, when used as a liquid, it may be a one-liquid type or two or more-liquid type. In addition, the curable resin composition of the present invention can be coated or impregnated with a sheet-like fibrous substrate such as glass cloth, glass, and nonwoven fabric such as amidine, and can be semi-hardened, that is, used as a prepreg.

The dry film of the present invention has a resin layer obtained by coating and drying a curable resin composition of the present invention on a film (supporting film). Here, when forming a dry film, the hardenable resin composition of the present invention is first diluted with the above-mentioned organic solvent and adjusted to an appropriate viscosity, and then a spot coater, a knife coater, a crack coater, a fixed rod coater, A compression coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, etc. are applied to the film with a uniform thickness. Thereafter, the coated composition is dried at a temperature of generally 40 to 130 ° C. for 1 to 30 minutes, whereby a resin layer can be formed. There is no particular limitation on the coating film thickness, but in general, the film thickness after drying is appropriately selected from the range of 3 to 150 μm, preferably 5 to 60 μm.

As the film (supporting film), a resin film is used. For example, a polyester film such as polyethylene glycol terephthalate (PET), a polyimide film, a polyimide film, or a polyimide film can be used. Acrylic film, polystyrene film, etc. There is no particular limitation on the thickness of this film, but it is generally appropriately selected from the range of 10 to 150 μm. A more preferable range is 15 to 130 μm.

In this way, for the film of the resin layer formed of the curable resin composition of the present invention, in order to prevent dust from adhering to the surface of the resin layer and the like, a film (protective film) that can be peeled off is further laminated on the surface of the resin layer. As the peelable film, any adhesive force between the resin layer and the support layer during peeling may be used as long as the adhesive force between the resin layer and the support film is smaller. For example, a polyethylene film or a polytetrafluoroethylene film, a polypropylene film, or a surface treatment can be used. Later paper and so on.

The hardened | cured material of this invention is obtained by hardening | curing the resin layer in the said curable resin composition of this invention, or the said dry film of this invention. Thus, the hardened | cured material of this invention can be used suitably as electronic component materials, such as a solder photoresist, an interlayer insulation material, and a buried hole material, which require insulation reliability.

The electronic component of the present invention includes the cured product of the present invention, and specific examples thereof include a printed wiring board. In particular, a multilayer printed wiring board using the curable resin composition of the present invention as an interlayer insulating material can have good interlayer insulation reliability.

<About the removal of the fine powder and other blending ingredients other than the fine powder of the second to fifth objects> In the first aspect of the present invention, the removal of the fine powder and the fines is related to the second to fifth objects. The other blending ingredients of the filler other than the powder are 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 one of a naphthalene skeleton and an onion skeleton as the curable resin. In this way, by using a cyclic ether compound having at least one of a naphthalene skeleton and an onion skeleton as an electronic component with a laminated structure, it is possible to suppress interlayer displacement and thereby obtain good interlayer insulation reliability. In particular, the present invention is useful in that the surface of the insulating layer roughened by the degreasing treatment is liable to cause displacement, and in this case, the reliability of the interlayer insulation is also easily ensured. In addition, the effect of reducing the thermal expansion property obtained by blending the fine powder can also be significantly exhibited in those having hydrophilicity in the fine powder. Such a fine powder has a large quantum effect on the properties of optical, electrical, and magnetic properties. Therefore, the physical properties such as reactivity and electrical properties can be easily changed and cause unexpected changes. This is the reason why the reliability of the insulation between the layers is poor when it is used as an electronic component with a multilayer structure. When the fine powder is hydrophilic particles such as fine cellulose fibers, the interlayer displacement becomes particularly poor. This problem can be solved by using a cyclic ether compound having at least one of a naphthalene skeleton and an onion skeleton.

[A cyclic ether compound having at least one of a naphthalene skeleton and an onion skeleton] A 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. The cyclic ether compound having a naphthalene skeleton is not particularly limited, but it is preferable to have two or more cyclic ethers in one molecule. This cyclic ether may also be a cyclic sulfide. Examples of commercially available products include Epiclon HP-4032, HP-4032D, HP-4700, HP-4770, HP-5000 (each of which is manufactured by DIC), NC-7000L, NC-7300L, NC -7700L (Either are manufactured by Nippon Kayaku Co., Ltd.), ZX-1355, ESN-155, ESN-185V, ESN-175, ESN-355, ESN-375, ESN-475V, ESN-485 (optional One is Nippon Steel & Sumikin Chemical Co., Ltd.).

A cyclic ether compound having an onion skeleton is a compound having a structure derived from an onion skeleton or an onion skeleton and having a cyclic ether. The cyclic ether compound having an onion skeleton is not particularly limited, but it is preferable to have two or more cyclic ethers in one molecule. This cyclic ether may also be a cyclic sulfide. Examples of commercially available products include YX-8800 (manufactured by Mitsubishi Chemical Corporation).

The blending amount of the cyclic ether compound having at least one of a naphthalene skeleton and an onion skeleton is preferably 0.5% by mass or more and 80% by mass or less with respect to the entire amount of the solvent-removing composition, and still more preferably 1 mass % To 40% by mass, more preferably 1.5% to 30% by mass. When the blending amount of the cyclic ether compound is 0.5% by mass or more, it is possible to prevent a decrease in interlayer insulation reliability caused by the fine cellulose fibers. On the other hand, when it is 80% by mass or less, the hardenability can be improved.

In the present invention, the above-mentioned cyclic ether compound having at least one of a naphthalene skeleton and an onion skeleton has a function as a hardening resin, and the cyclic ether compound having a naphthalene skeleton and the cyclic ether compound having an onion skeleton may be used alone or in combination. Cyclic ether compounds.

In the present invention, if desired, a curable resin such as a thermosetting resin or a photocurable resin other than a cyclic ether compound having at least one of a naphthalene skeleton and an onion skeleton may be used in combination.

Regarding the third object of the present invention, the curable resin composition of the present invention is formed from a cyclic ether compound having a dicyclopentadiene skeleton and a phenol resin having a dicyclopentadiene skeleton as a curable resin. At least one species in the group is preferred. Therefore, 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 permittivity and the loss factor can be reduced to obtain Electronic components with low dielectric properties. On the other hand, by using a fine powder, the adhesion between the hardened material and the plated copper can be ensured, and a high-definition circuit can be formed. In addition, the fine powder used in the present invention can be obtained by blending a hardening resin having a dicyclopentadiene skeleton having low adhesion to plated copper, thereby achieving adhesion with plated copper. A very high hardened product containing a composition related to a hardenable resin. Moreover, obtaining this effect does not reduce the dielectric characteristics derived from the dicyclopentadiene skeleton.

[Cyclic ether compound with dicyclopentadiene skeleton and phenol resin with dicyclopentadiene skeleton] Cyclic ether compound with dicyclopentadiene skeleton has a dicyclopentadiene skeleton or dicyclopentadiene It has a structure of an ene skeleton and is a compound having a cyclic ether. The cyclic ether compound having a dicyclopentadiene skeleton is not particularly limited, but it is preferable to have two or more cyclic ethers in one molecule. This cyclic ether may also be a cyclic sulfide. Examples of commercially available products include Epiclon HP-7200, HP-7200H, HP-7200L (each of which is made by DIC), XD-1000-1L, and XD-1000-2L (which are both Nippon Kayaku Co., Ltd.), Tactix558, Tactix756 (Each one is manufactured by Huntsman Advanced Materials) and the like.

A phenol resin having a dicyclopentadiene skeleton has a structure derived from a dicyclopentadiene skeleton or a dicyclopentadiene skeleton, and is a compound having a phenolic hydroxyl group. The phenol resin having a dicyclopentadiene skeleton is not particularly limited, but it is preferable to have two or more phenolic hydroxyl groups in one molecule. As commercial products, Resitop GDP-6085, Resitop GDP-6095LR, Resitop GDP-6095HR, Resitop GDP-6115L, Resitop GDP-6115H, Resitop GDP-6140 (Either are manufactured by Qunrong Chemical Industry Co., Ltd.), J- DPP-95, J-DPP-115 (either of which is manufactured by JFE Chemical Co., Ltd.), and the like.

The blending amount of 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 preferably the total amount of the composition from which the solvent is removed, 0.5 mass% to 80 mass%, more preferably 1 mass% to 40 mass%, more preferably 1.5 mass% to 30 mass%. When the mixing amount of 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 0.5% by mass or more, good low dielectric properties can be obtained. characteristic. On the other hand, when it is 80% by mass or less, the hardenability can be improved.

In the present invention, 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 has a function as a curable resin, and can also be used individually. Alternatively, a cyclic ether compound having a dicyclopentadiene skeleton and a phenol resin having a dicyclopentadiene skeleton may be used in combination.

In the present invention, a thermosetting resin or light 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 can be used in combination, as desired. A curable resin such as a curable resin.

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. Therefore, by using a phenoxy resin and a fine powder, the stain can be removed in a short time during the stain removal step, and the surface roughness of the hardened material can be suppressed to a small level, and high frequency can be efficiently transmitted. On the other hand, since the surface roughness is small, the adhesion between the hardened material and the plated copper can be ensured, so that a high-definition circuit can be formed. In addition, by using the fine powder related to the present invention, the hardened material of the composition containing the related fine powder can easily remove stains, and while suppressing the surface roughness of the hardened material to be small, it can also ensure that Copper adhesion. This effect is exhibited by a combination with a phenoxy resin described later. In addition, this effect can significantly express hydrophilicity even in a fine powder.

[Phenoxy Resin] Phenoxy resin is generally synthesized from bisphenols and epichlorohydrin. The bisphenols used are bisphenol A type, bisphenol F type, bisphenol S type, biphenyl type, bisphenol acetophenone type, amidine type, trimethylcyclohexane type, terpene type, etc. These are two or more types of copolymerization. The phenoxy resin is not particularly limited, but when used as a photocurable composition, a terminal epoxy type is preferred. Examples of commercially available products include 1256, 4250, 4275, YX8100, YX6954, YL7213, YL7290, YL7482 (any one is made by Mitsubishi Chemical Corporation), FX280, FX293, YP50, YP50S, YP55, YP70, YPB- 43C (Each one is manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), PKHB, PKHC, PKHH, PKHJ, PKFE, PKHP-200, PKCP-80 (any one is manufactured by InChem), and the like.

The blending amount of the phenoxy resin is preferably 0.1% by mass or more and 50% by mass or less with respect to the entire amount of the solvent-removing composition, more preferably 0.3% by mass or more and 30% by mass or less, and more preferably 0.5% by mass. Above 10% by mass. When the blending amount of the phenoxy resin is 0.1% by mass or more, the removability of the stain caused by the fine powder and the adhesiveness of the conductor are improved. On the other hand, when it is 50 mass parts or less, hardenability improves.

In the present invention, it is possible to further use a curable resin such as a thermosetting resin other than a phenoxy resin or a photocurable resin in combination, as desired.

Regarding the fifth object of the present invention, the curable resin composition of the present invention contains, 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. good. Therefore, by using 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, when forming solid copper plating on a hardened product, it is possible to suppress the occurrence of component defects. Expansion caused by the thermal history of the installation and the copper plating. In addition, the effect of reducing the thermal expansion caused by blending the fine powder can significantly exhibit hydrophilicity even in the fine powder. On the other hand, when the fine powder is, for example, hydrophilic particles such as fine cellulose fibers, the application of the present invention is particularly useful in view of the high temperature expansion easily caused by the solid copper plating.

[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] A cyclic ether compound having a biphenyl skeleton has a structure derived from a biphenyl skeleton or a biphenyl skeleton, and It is a compound having a cyclic ether. The cyclic ether compound having a biphenyl skeleton is not particularly limited, but it is preferable to have two or more cyclic ethers in one molecule. This cyclic ether may also be a cyclic sulfide. Examples of commercially available products include NC-3000H, NC-3000L, NC-3100 (all of which are manufactured by Nippon Kayaku Co., Ltd.), YX-4000, YX4000H, and YL-6121 (all of which are Mitsubishi Chemical (stock) system), Denacol EX-412 (Nagase ChemteX (stock) system), etc.

The blending amount of the cyclic ether compound having a biphenyl skeleton is preferably 0.5% by mass or more and 80% by mass or less, and more preferably 1% by mass or more and 40% by mass or less with respect to the entire amount of the solvent-removing composition. It is preferably 1.5% by mass or more and 30% by mass or less. When the compounding amount of the compound is 0.5% by mass or more, swelling of the plated copper due to fine particles can be prevented. On the other hand, when it is 80% by mass or less, the hardenability is improved.

A phenol resin having a biphenyl skeleton has a structure derived from a biphenyl skeleton or a biphenyl skeleton, and is a compound having a phenolic hydroxyl group. The phenol resin having a biphenyl skeleton is not particularly limited, but it is preferable to have two or more phenolic hydroxyl groups in one molecule. Examples of commercially available products include GPH-65, GPH-103 (manufactured by Nippon Kayaku Co., Ltd.), MEH-7851SS, MEH-7851M, MEH-7851-4H, and MEH-7851-3H (Meiwa Kasei Co., Ltd.) System), HE200 (Air Water (stock) system), etc.

The blending amount of the phenol resin having a biphenyl skeleton is preferably 0.5% by mass or more and 60% by mass or less, and more preferably 1% by mass or more and 30% by mass or less with respect to the total amount of the solvent-removing composition. It is 1.5 mass% or more and 20 mass% or less. When the compounding amount of the compound is 0.5% by mass or more, swelling of the plated copper due to fine particles can be prevented. On the other hand, when it is 60 mass% or less, hardenability improves.

In the present invention, at least one selected from the group consisting of the above-mentioned cyclic ether compound having a biphenyl skeleton and a phenol resin having a biphenyl skeleton has a function as a curable resin, and may be used alone or in combination with a biphenyl skeleton. A cyclic ether compound and a phenol resin having a biphenyl skeleton.

In the present invention, as desired, it is possible to use in combination a curable resin such as a thermosetting resin or a photocurable resin selected from the group consisting of a cyclic ether compound having a biphenyl skeleton and a phenol resin having a biphenyl skeleton. Resin.

(Thermosetting resin) As the thermosetting resin, any resin that hardens due to heating and shows electrical insulation properties may be used. Examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type. Epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol Z type epoxy resin, etc. Varnish type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, varnish type epoxy resin, biphenyl type epoxy resin, biphenylarane type epoxy resin, aryl alkane type epoxy resin, tetrahydroxy Phenylethane type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, original norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, glycidyl methyl ester Acrylate copolymer epoxy resin, cyclohexyl maleimide and glycidyl methacrylate copolymer epoxy resin, epoxy modified polybutadiene rubber derivative, CTBN modified epoxy resin , Trimethylolpropane glycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4'-di Glycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitan glycidyl ether, ginseng (2,3-epoxypropyl) isocyanate, triglycidyl Ginseng (2-hydroxyethyl) isocyanate, novolac resin, cresol novolac resin, bisphenol A novolac resin, etc., varnish-type phenol resin, unmodified phenolic resin, retinol, linseed oil, walnut Oils modified by oils, etc., phenol resins such as resol phenol resins, phenol resins such as phenol resins, phenoxy resins, urea resins, melamine resins, and resins containing triazine rings, Unsaturated polyester resin, bismaleimide resin, diallyl phthalate resin, siloxane resin, resin with benzoxazine ring, orthobornene resin, cyanate resin, Isocyanate resin, urethane resin, benzocyclobutene resin, maleimide resin, bismaleimide triazine resin, polyazomethyl resin, thermosetting polyimide resin, Cyclopentadienyl diphenol ester compound, bisphenol A diacetate, diphenyl phthalate , Terephthalic acid, diphenyl terephthalate, bis [4- (methoxycarbonyl) phenyl] ester, etc. an active compound. Among them, the use of an active ester compound is preferred because it can reduce the thermal expansion in a high-temperature region and ensure a low thermal expansion rate.

(Photocurable resin (radical polymerization)) As a related photocurable resin, any resin that hardens due to irradiation with active energy rays and exhibits electrical insulation properties may be used, and it is particularly preferable to use one or more ethylenic molecules in the molecule. Unsaturated compounds. Examples of the compound having an ethylenically unsaturated bond include a well-known and commonly used photopolymerizable oligomer and a photopolymerizable ethylene monomer.

Examples of the photopolymerizable oligomer include unsaturated polyester-based oligomers and (meth) acrylate-based oligomers. Examples of the (meth) acrylate-based oligomer include novolak epoxy (meth) acrylate, cresol novolak epoxy (meth) acrylate, bisphenol epoxy (meth) acrylate, and the like Epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) ) Acrylate, polybutadiene modified (meth) acrylate and the like. In addition, in this specification, (meth) acrylate means the term of an acrylate, a methacrylate, and these mixtures collectively, and it is the same about other similar expressions.

Examples of the photopolymerizable ethylene monomer include styrene derivatives such as styrene, chlorostyrene, and α-methylstyrene, and vinyl esters such as vinyl acetate, vinyl caseinate, and vinyl benzoate. ; Vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-pentyl ether, vinyl isoamyl ether, vinyl-n-octadecyl Ethers, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether, and other vinyl ethers; ammonium acrylate, ammonium methacrylate, and N-hydroxymethyl Ammonium acrylate, N-hydroxymethyl methylpropionate, N-methoxymethacrylate, N-ethoxymethacrylate, N-butoxymethacrylate, etc. (Meth) acrylic acid amines; triallyl isocyanate, diallyl phthalate, diallyl isophthalate and other allyl compounds; 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isofluorenyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl ( (Meth) acrylic esters such as (meth) acrylates; hydroxyalkyl (such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, etc. (Meth) acrylates; alkoxyalkylene glycol mono (meth) acrylates, such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, etc; Alcohol di (meth) acrylates, butanediol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate , Poly (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc .; diethylene glycol Alcohol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri (meth) acrylate Poly (meth) acrylates such as polyoxyalkylene glycols; poly (meth) acrylates such as hydroxyvaleric acid neopentyl glycol di (meth) acrylates; see [(甲base) Isocyanate-type poly (meth) acrylates and the like such as acrylfluorenyloxyethyl] isocyanate and the like.

(Photocurable resin (cationic polymerization)) As the related photocurable resin, an alicyclic epoxy compound, a propylene oxide compound, a vinyl ether compound, and the like can be appropriately used. Examples of the alicyclic epoxy compound include 3,4,3 ', 4'-diepoxydicyclohexyl ester, 2,2-bis (3,4-epoxycyclohexyl) propane, and 2,2 -Bis (3,4-epoxycyclohexyl) -1,3-hexafluoropropane, bis (3,4-epoxycyclohexyl) methane, 1- [1,1-bis (3,4-epoxy ring Hexyl)] ethylbenzene, bis (3,4-epoxycyclohexyl) adipate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane carboxylate, (3 , 4-Epoxy-6-methylcyclohexyl) methyl-3 ', 4'-epoxy-6-methylcyclohexanecarboxylate, ethylidene-1,2-bis (3,4- Epoxy cyclohexane carboxylate), epoxy cyclohexane, 3,4-epoxycyclohexylmethyl alcohol, 3,4-epoxycyclohexylethyltrimethoxysilane, etc. Cycloepoxy compounds and the like. Examples of commercially available products include Celloxide 2000, Celloxide 2021, Celloxide 3000, and EHPE3150 manufactured by Daicel Chemical Industries (stock); Epico VG-3101 manufactured by Mitsui Chemicals (stock); and E- manufactured by Petrochemical Shell Epoxy (stock) 1031S; TETRAD-X and TETRAD-C made by Mitsubishi Gas Chemical Co., Ltd .; EPB-13 and EPB-27 made by Soda Japan.

Examples of the propylene oxide compound include bis [(3-methyl-3-glycidyloxy) methyl] ether and bis [(3-ethyl-3-glycidyloxy). Methyl] ether, 1,4-bis [(3-methyl-3-glycidyloxy) methyl] benzene, 1,4-bis [(3-ethyl-3-glycidyloxy) (Methoxy) methyl] benzene, (3-methyl-3-glycidyl) methacrylate, (3-ethyl-3-glycidyl) methacrylate, (3-methyl Multifunctional epoxy resins such as -3-glycidyl) methacrylate, (3-ethyl-3-glycidyl) methacrylate, or oligomers or copolymers thereof In addition to propane, there are also hydroxyl-containing resins such as propylene oxide and varnish resins, poly (p-hydroxystyrene), Cardo-type bisphenols, calixarenes, resorcinol calixarenes, or semisiloxanes. Ether compounds of resins, propylene oxide compounds such as copolymers of unsaturated monomers having an propylene oxide ring and alkyl (meth) acrylates. As commercially available products, there are, for example, Eternacoll OXBP, OXMA, OXBP, EHO, xylylene dipropylene oxide manufactured by Ube Kosan Co., Ltd., and Aron oxetane OXT-101, OXT-201 manufactured by Toa Kosei Co., Ltd. , OXT-211, OXT-221, OXT-212, OXT-610, PNOX-1009, etc.

Examples of vinyl ether compounds include cyclic ether vinyl ethers (such as ethylene oxide ring, propylene oxide ring, and oxypentane ring), such as isosorbide divinyl ether and oxaorbornene divinyl ether. Vinyl ethers with cyclic ether groups); aryl vinyl ethers such as phenyl vinyl ether; alkyl vinyl ethers such as n-butyl vinyl ether and octyl vinyl ether; cyclohexyl vinyl Ethers such as cycloalkyl vinyl ethers; hydroquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexane divinyl ether, cyclohexane dimethanol divinyl ether, etc. Functional vinyl ether, α and / or vinyl ether compounds having a substituent such as an alkyl group or an allyl group at the β position, and the like. Examples of commercially available products include 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), and 2-hydroxybutyl vinyl ether (HBVE) manufactured by Maruzan Petrochemical Co., Ltd. ), Triethylene glycol divinyl ether, and the like.

In addition, when the photoresist of an alkaline developing type capable of developing the curable resin composition of the present invention in an alkaline aqueous solution is used, a carboxyl group-containing resin is preferably used.

(Carboxyl-containing resin) As the carboxyl-containing resin, a photosensitive carboxyl-containing resin having one or more photosensitive unsaturated double double bonds and a carboxyl-containing resin having no photosensitive unsaturated double bond can be used. Either is not limited to a special one. As the carboxyl group-containing resin, in particular, the resins listed below can be suitably used. (1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and a compound having an unsaturated double bond, and a carboxyl group-containing resin whose molecular weight or acid value is modified by modifying it. (2) A photosensitive carboxyl group-containing resin obtained by reacting a carboxyl group-containing (meth) acrylic copolymer resin with a compound having an ethylene oxide ring and an ethylenically unsaturated group in one molecule. (3) A copolymer of a compound having an epoxy group and an unsaturated double bond and a compound having an unsaturated double bond, respectively, in one molecule is reacted with an unsaturated monocarboxylic acid, so that the second order produced by the reaction A photosensitive carboxyl group resin obtained by reacting a hydroxyl group with a saturated or unsaturated polybasic acid anhydride. (4) Photosensitivity obtained by reacting a hydroxyl-containing polymer with a saturated or unsaturated polybasic acid anhydride, and reacting a carboxylic acid formed by the reaction with a compound having one epoxy group and an unsaturated double bond in each molecule. Resin containing hydroxyl and carboxyl groups. (5) A photosensitive carboxyl group-containing resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting a part or all of the second-stage hydroxyl group formed by the reaction with a polybasic acid anhydride. (6) A polyfunctional epoxy compound is reacted with a compound having one reactive group other than a hydroxyl group having two or more hydroxyl groups and epoxy groups in one molecule, reacted with an unsaturated monocarboxylic acid, and then Carboxyl-containing photosensitive resin obtained by reacting the obtained reaction product with a polybasic acid anhydride. (7) The reaction product obtained by reacting a resin having a phenolic hydroxyl group with an alkylene oxide or a cyclic carbonate with an unsaturated monocarboxylic acid, and then reacting the obtained reaction product with a polybasic acid anhydride Carboxyl photosensitive resin. (8) A polyfunctional epoxy compound is reacted with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule with an unsaturated monocarboxylic acid, and then the alcohol of the obtained reaction product is reacted. A carboxyl group-containing photosensitive resin obtained by reacting a hydroxyl group with an anhydride group of a polybasic acid anhydride.

[Filler] It is preferred that the curable resin composition of the present invention further contains a filler other than fine powder. Examples of the filler include barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, white clay, magnesium carbonate, calcium carbonate, alumina, and hydrogen. Alumina, silicon nitride, aluminum nitride, etc. Among these fillers, from the viewpoint of being low in specific gravity, being able to be blended in the composition at a high ratio, and being excellent in low thermal expansion, silicon dioxide is preferred, and spherical silicon dioxide is preferred. The average particle diameter of the filler is preferably 3 μm or less, and more preferably 1 μm or less. The average particle diameter of the filler can be determined by a laser diffraction type particle diameter distribution measuring device.

The blending amount of the filler is 1 to 90% by mass, preferably 2 to 80% by mass, and still more preferably 5 to 75% by mass of the entire amount of the composition from which the solvent is removed. By setting the blending amount of the filler within the above range, the coating film performance of the hardened product after hardening can be well ensured.

In the curable resin composition of the present invention, other conventional blending ingredients can be appropriately blended in accordance with its use. Examples of other commonly used blending ingredients include hardening catalysts, photopolymerization initiators, colorants, and organic solvents.

Examples of the curing catalyst include phenol compounds; imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1- Cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, and other imidazole derivatives; dicyandiamine, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethyl Amine compounds such as benzylamine, hydrazine compounds such as dihydrazine adipate, dihydrazine sebacate, and phosphorus compounds such as triphenylphosphine. In addition, as commercially available products, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (made by Shikoku Chemical Industry Co., Ltd.), U-CAT3503N, U-CAT3502T, DBU, DBN, U-CATSA102, U-CAT5002 (made by San Apro) can be used alone or in combination of two or more. In addition, similarly, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacrylamidooxyethyl-S-triazine, and 2-ethylene can also be used. -2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine • isocyanuric acid adduct, 2,4-diamino- S-triazine derivatives such as 6-methacrylfluorenyloxyethyl-S-triazine and isotricyanic acid adducts.

In the present invention, a phenol compound is preferably used among them. As a phenol compound, a phenol novolak resin, an alkyl novolak resin, a triazine-containing varnish resin, a bisphenol A varnish resin, a dicyclopentadiene type phenol resin, and a Zyloric type phenol can be used alone or in combination. Resins, Copna resins, terpene modified phenol resins, phenol compounds such as polyvinyl phenols, naphthalene-based hardeners, and fluorene-based hardeners are known and commonly used. Examples of the phenol compounds include HE-610C, 620C manufactured by Air Water, and TD-2131, TD-2106, TD-2093, TD-2091, TD-2090, and VH-4150 made by DIC (stock). , VH-4170, KH-6021, KA-1160, KA-1163, KA-1165, TD-2093-60M, TD-2090-60M, LF-6161, LF-4871, LA-7052, LA-7054, LA -7751, LA-1356, LA-3018-50P, EXB-9854, SN-170, SN180, SN190, SN475, SN485, SN495, SN375, SN395, JX Nippon Steel & Nippon Stone Energy DPP, Meiwa Chemicals HF-1M, HF-3M, HF-4M, H-4, DL-92, MEH-7500, MEH-7600-4H, MEH-7800, MEH -7851, MEH-7851-4H, MEH-8000H, MEH-8005, XL, XLC, RN, RS, RX, etc. manufactured by Mitsui Chemicals Co., Ltd., but not limited to these. These phenol compounds can be used individually or in combination of 2 or more types.

The blending amount of the hardening catalyst used in the present invention is sufficient as long as it is generally used, and it is 1 to 150 parts by mass, and preferably 5 to 100 parts by mass with respect to 100 parts by mass of the thermosetting resin. 100 parts by mass, more preferably 10 to 50 parts by mass, and in the case of other hardening catalysts, 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass.

The photopolymerization initiator is used to harden the photocurable resin in the curable resin, and may also be a photoradical polymerization initiator or a photocationic polymerization initiator. Examples of photoradical polymerization initiators include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy 2-acetophenones such as 2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butane Ketone-1, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morphoyl) phenyl] -1-butanone, etc. Amino alkyl phenones; 2-methyl shallots, 2-ethyl shallots, 2-tert-butyl shallots, 1-chloro shallots, etc .; 2,4-dimethyl Thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and other thioxanthone; acetophenone dimethyl ketal, benzyl Ketals such as dimethyl ketals; diphenyl ketones such as diphenyl ketones; or ketans; (2,6-dimethoxybenzyl) -2,4,4- N-pentylphosphine oxide, bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide, 2,4,6-trimethylbenzylidene diphenylphosphine oxide Phosphine oxides, such as ethyl-2,4,6-trimethylbenzylidenephenyl phosphinate; various peroxides, titanium rhenium starters, etc. These may also be used in combination with N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, n-pentyl-4-dimethylaminobenzoic acid Ester, triethylamine, triethanolamine, etc., such as tertiary amines, photosensitizers, etc.

Examples of photocationic polymerization initiators include onium salts such as diazonium salts, phosphonium salts, bromium salts, chloronium salts, sulfonium salts, selenium salts, pyran salts, thiopyran salts, and pyridine salts; (Trihalomethyl) -s-triazines and their halogenated compounds, etc .; 2-nitrobenzyl esters of sulfonic acid; imine disulfonic acid; 1-oxo-2-diazonaphthoquinone- 4-sulfonate derivatives; N-hydroxyphosphonium imine = sulfonic esters; tris (methanesulfonyloxy) benzene derivatives; bissulfonyldiazomethanes; sulfonylcarbonylalkanes; sulfonyl Fluorenylcarbonyldiazomethanes; difluorene compounds and the like. These photopolymerization initiators can be used alone or in combination of two or more kinds.

The blending amount of the photopolymerization initiator is calculated in terms of solid content, and is, for example, 0.05 to 10 parts by mass, preferably 0.1 to 8 parts by mass, and still more preferably 0.3 to 6 parts by mass relative to 100 parts by mass of the photocurable resin. By blending a photopolymerization initiator within this range, the photo-hardening properties on copper will be sufficient, the hardening properties of the coating film will be better, the coating film properties such as chemical resistance will be improved, and the deep hardening properties will also be improved. .

As the colorant, conventionally known coloring agents such as red, blue, green, and yellow can be used, and any of pigments, dyes, and pigments may be used. However, from the viewpoint of reducing the environmental load and the impact on the human body, it is preferable not to contain halogen.

Blue coloring agent: As a blue coloring agent, there are titanium cyanine series, scallion onion series, and pigments are compounds classified as pigments. Specific examples include the following color index (CI; dyeing) And The Society of Dyersand Colourists) Number: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16. PigmentBlue 60. As the 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 and so on. In addition to the above, metal-substituted or unsubstituted titanium cyanine compounds can also be used.

Green colorants: As green colorants, there are also titanium cyanine series and scallion onion series. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. can be used. . In addition to the above, metal-substituted or unsubstituted titanium cyanine compounds can also be used.

Yellow colorants: As yellow colorants, there are monoazo-based, diazo-based, condensed azo-based, benzimidazolone-based, isoindolinone-based, scallion-onion-based, and the like. Specific examples include the following: . Allium: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202. Isoisoindolinone series: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185. Condensed azo series: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180. Pyridoxazoles: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181. Monoazo: 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. Diazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

Red colorants: As red colorants, there are monoazo-based, diazo-based, azo lake-based, benzimidazolone-based, fluorene-based, diketopyrrolopyrrole-based, condensed azo-based, scallion-onion-based, Specific examples of quinacridones include the following. Monoazo: 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. Diazo: 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. Pyridoxazolones: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208. System: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224. Perylene diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272. Condensed azo series: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.菎 Allium: Pigment Red 168, PigmentRed 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207. Acquinone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

In addition, for the purpose of adjusting hue, colorants such as purple, orange, brown, and black may be added. Specific examples include 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 Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black 7, etc.

The specific blending ratio of the colorant can be appropriately adjusted depending on the type of the colorant used or other types of additives.

Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; methyl cyrus, ethyl cyrus, butane Kiselosulfone, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, etc. Alcohol ethers; Ethyl acetate, butyl acetate, celex acetate, diethylene glycol monoethyl ether acetate, and esters of the above-mentioned glycol ethers; ethanol, propanol, ethyl Alcohols such as diols and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and solvent oil.

Furthermore, if necessary, it can contain well-known and conventional additives, such as a defoamer, a leveler, a shake-miscibility imparting agent, a thickener, a coupling agent, a dispersing agent, and a flame retardant.

The curable resin composition of the present invention can also be used as a dry film or as a liquid. In addition, the curable resin composition of the present invention can be applied as a prepreg by coating or impregnating sheet-like fibrous substrates such as glass cloth, glass, and nonwoven fabrics such as ammonium, and semi-hardening it. When it is used as a liquid, it may be one-liquid or two-liquid or more. As the two-liquid composition, for example, it can be used as a composition, which is divided into: fine cellulose fibers, and at least one selected from the group consisting of a cyclic ether compound having a naphthalene skeleton and a cyclic ether compound having an onion skeleton. 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, a phenoxy resin, or a cyclic ether compound having a biphenyl skeleton And at least one of a group of phenol resins having a biphenyl skeleton.

The dry film of the present invention has a resin layer obtained by coating and drying the curable resin composition of the present invention on a carrier film. When forming a dry film, first dilute the curable resin composition of the present invention with the above-mentioned organic solvent and adjust it to an appropriate viscosity, and then use a spot coater, a doctor blade coater, a crack coater, a fixed rod coater, and a compression coater. , Reverse coater, transfer cylinder coater, gravure coater, spray coater, etc., to coat the carrier film with a uniform thickness. Thereafter, the coated composition is dried at a temperature of generally 40 to 130 ° C. for 1 to 30 minutes, whereby a resin layer can be formed. There is no particular limitation on the coating film thickness, but in general, the film thickness after drying is appropriately selected from the range of 3 to 150 μm, preferably 5 to 60 μm.

As the carrier film, there are plastic films, for example, polyester films such as polyethylene glycol terephthalate (PET), polyimide films, polyimide films, polypropylene films, Polystyrene film, etc. The thickness of the carrier film is not particularly limited, but is generally appropriately selected from a range of 10 to 150 μm. A more preferable range is 15 to 130 μm.

After forming a resin layer made of the curable resin composition of the present invention on a carrier film, it is preferable to further laminate a cover film capable of peeling on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. As the cover film, when the cover film is peeled off, the adhesive force with the resin layer may be smaller than the adhesive force between the resin layer and the carrier film.

Furthermore, in the present invention, a resin layer may be formed by coating and drying the curable resin composition of the present invention on the cover film, and the film may be carried on the surface area layer. That is, when the dry film is produced in the present invention, as the film to which the curable resin composition of the present invention is applied, either a carrier film or a cover film may be used.

The hardened | cured material of this invention is obtained by hardening | curing the resin layer in the said curable resin composition of this invention, or the said dry film of this invention.

The electronic component of the present invention includes the cured product of the present invention, and specific examples thereof include a printed wiring board. The hardened | cured material of this invention can be used suitably for the electronic component which requires insulation reliability between layers. In particular, a multilayer printed wiring board using the curable resin composition of the present invention as an interlayer insulating material can have good interlayer insulation reliability.

Fig. 2-1 (Fig. 3-1, Fig. 4-1, Fig. 5-1) is a partial cross-sectional view showing a configuration example of a related multilayer printed wiring board shown as an example of an electronic component of the present invention. The multilayer printed wiring board shown in the figure can be manufactured, for example, as follows. First, a through hole is formed in the core substrate 2 on which the conductor pattern 1 is formed. The formation of the through hole can be performed by a suitable means such as a drill, a gold punch, and laser light. After that, a roughening treatment is performed using a roughening agent. Generally, the roughening treatment is an organic solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, and methoxypropanol, or an alkaline aqueous solution such as caustic caustic soda and caustic potassium. Swell it and use oxidants such as dichromate, permanganate, ozone, hydrogen peroxide / sulfuric acid, and nitric acid.

Next, a conductor pattern 3 is formed by electroless plating or a combination of electrolytic plating and the like. The step of forming a conductor layer by electroless plating is a step of immersing in an aqueous solution containing a plating catalyst, absorbing the catalyst, and immersing it in a plating solution to precipitate the plating. According to a common method (elimination method, semi-additive method, etc.), a specific circuit pattern is formed on the conductor layer on the surface of the core substrate 2, and a conductor pattern 3 is formed on both sides as shown in the figure. At this time, a plating layer is also formed in the through holes. As a result, the connection portion 4 of the conductor pattern 3 of the multilayer printed wiring board and the connection portion 1 a of the conductor pattern 1 are electrically connected to form a through hole 5.

Next, the interlayer insulating layer 6 is formed by applying a suitable method such as a screen printing method, a spray coating method, or a curtain coating method, for example, after applying a thermosetting composition and curing it by heating. When a dry film or a prepreg is used, bonding or hot-plate pressing is performed, and it is heated and hardened to form an interlayer insulating layer 6. Next, the dielectric layer 7 for electrically connecting the connection portions between the conductor layers is formed by an appropriate means such as laser light, and the conductor pattern 8 is formed in the same manner as the conductor pattern 3 described above. Furthermore, the interlayer insulating layer 9, the interlayer 10, and the conductor pattern 11 are formed in the same manner. Thereafter, a multilayered printed wiring board is manufactured by forming the solder photoresist layer 12 as the outermost layer. In the above, an example in which an interlayer insulating layer and a conductor layer are formed on a multilayer substrate has been described, but a single-sided substrate or a double-sided substrate may be used instead of the multilayer substrate.

<<< Second Form of the Present Invention >> 硬化 The curable resin composition of the second form of the present invention is characterized in that it contains (A) a fine powder having a size smaller than 100 nm at least once, and (B) a thermosetting component. . With the characteristic configuration of the second form of the present invention, the unique effect of this case can be exerted. The effect is that in a printed wiring board having at least one of a recessed portion and a through hole, even during high-temperature heating during component mounting, Recesses such as through-holes or through-holes filled with resin filler or conductor pads or through-holes on the through-holes do not swell. The detailed mechanism of wiring expansion caused by this high-temperature heating is unknown, and it is thought that the difference between the thermal expansion coefficient of the through hole or through hole formed of copper and the resin filler at high temperature is large. In general, in order to make organic substances such as resins smaller to the thermal expansion coefficient of metals, there are well-known methods of mixing inorganic fillers in large quantities. By this method, the thermal expansion coefficient close to normal temperature can indeed be close to that of metal, but when the component is heated at high temperature, even if it contains a large amount of filler, the thermal expansion coefficient will still be much larger than that of metal. Therefore, it is considered that the resin filler swells up and down the through hole when heated at a high temperature, for example. In addition, the reliability of the wall surface of the through-hole or the bottom of the through-hole that suppresses swelling is reduced due to the application of pressure. From this point of view, it is believed that with the present invention, since fine powders such as fine cellulose fibers are dispersed in a resin filler, the fine powders will have a mutual effect of pulling each other, thereby exhibiting a reinforcing effect, even in It is possible to suppress a rise in the coefficient of thermal expansion even at high temperature heating, and as a result, a unique effect is obtained in that the wiring does not swell due to high temperature heating.

In addition, according to the characteristic structure of the second aspect of the present invention, in a method for manufacturing a printed wiring board having at least one of a recess and a through hole, when the curable resin composition filled in the recess or the through hole is cured, A unique effect of the present invention is that the filler component does not ooze out a thin resin composition.详细 The detailed mechanism of the thin resin component exudation of the filler component at the time of hardening is unknown, but it is thought that it is because the liquid component must be used as the resin component in order to adjust the viscosity. It is desirable that resin fillers filled in recesses or through holes such as through holes or through holes do not use solvents with volatile components. When such liquid resin components are used, if they are heated to harden, the viscosity before the hardening reaction will decrease. Due to the capillary phenomenon, the resin component will ooze out along the side of the copper foil. This is because, according to the second aspect of the present invention, since the fine powder such as fine cellulose fibers is dispersed in the resin filler, the reinforcing effect is exhibited by the mutual effect of the aforementioned fine powders. Moreover, the viscosity at the time of standing can be maintained even after being heated at a high temperature, and the special effect that the resin component is hardened before oozing out of the copper foil is obtained.

In addition, according to the characteristic configuration of the present invention, in a printed wiring board having at least one of a recessed portion and a through hole, a polishing step after curing of the curable resin composition filled in the recessed portion or the through hole can be used. The present invention has a unique effect of producing depressions such as holes and the like caused by excessive polishing for smoothing. Regarding the recesses or through-holes in this grinding step, the detailed mechanism is not clear. The resin filler is used to completely fill the recesses or through-holes such as the through-holes or through-holes. And the upper part of the through-hole (Fig. 7-4 (a)), heat-harden it, and remove unnecessary parts with a polishing roller or the like in the grinding step. However, the resin filler which is thus heat-cured is deformed when applied with pressure, so it is easy to generate residue (Fig. 7-4 (b)). At this time, the grinding conditions are made stricter so that the resin filler is excessively removed after grinding without leaving any residue, so that a depression is generated in the through-hole portion (Fig. 7-4 (c)). This is because, according to the second aspect of the present invention, since the fine powder such as fine cellulose fibers is dispersed in the resin filler, the reinforcing effect is exhibited by the mutual effect of the aforementioned fine powders. In addition, the strength of the resin is increased, so that the unique effect of reducing the pressure deformation and uniformly grinding can be obtained. Hereinafter, a second embodiment of the present invention will be described in detail.

[(A) Fine powder] As the fine powder used in the second aspect of the present invention, the same one as described in the first aspect can be used. By using such a fine powder and using a curable resin composition containing the relevant fine powder as a resin filler for filling pores and the like, the mutual effect of the fine powders pulling on each other can be obtained, thereby Since it exhibits a reinforcing effect, as described above, it is difficult to cause swelling after high-temperature heating or bleeding of resin components, and it is also difficult to generate depressions of fillers filled in holes and the like during the polishing step to form hardened materials. In addition, this effect can be remarkably exhibited even in a fine powder.

[(B) Thermosetting component] The thermosetting component is not particularly limited, but a compound having two or more cyclic ethers in one molecule is preferred. This cyclic ether may also be a cyclic sulfide. The cyclic ether compound may be used alone or in combination of two or more. Among such cyclic ether compounds, epoxy resins and propylene oxide resins are preferred, and epoxy resins are particularly preferred.

As the epoxy resin, a known epoxy resin can be used. For example, as the thermosetting resin, as long as it is a resin which hardens due to heating and shows electrical insulation, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol Bisphenol E epoxy resin, bisphenol M epoxy resin, bisphenol P epoxy resin, bisphenol Z epoxy resin, bisphenol epoxy resin, bisphenol A varnish epoxy resin, phenol varnish Type epoxy resin, cresol varnish epoxy resin, varnish type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, onion type epoxy resin, biphenylarane type epoxy resin, aryl butane Type epoxy resin, tetrahydroxyphenylethane type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, original norbornene type epoxy resin, adamantane type epoxy resin, fluorene type Epoxy resin, glycidyl methacrylate copolymer epoxy resin, cyclohexyl maleimide and glycidyl methacrylate ester copolymer epoxy resin, epoxy modified polybutadiene rubber derivative , CTBN modified epoxy resin, trimethylolpropane glycidyl 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 glycidyl ether, ginseng (2,3-cyclo (Oxypropyl) isocyanate, triglycidyl (2-hydroxyethyl) isocyanate, and the like.

As the curable resin composition of the present invention, the dispersibility of fine powder such as fine cellulose fibers can be improved by mixing an epoxy resin having amines as precursors as the epoxy resin. Specifically, when manufacturing a fine powder dispersion, the fluidity will increase and the viscosity can be reduced. Therefore, the workability will be improved and the viscosity of the composition will be reduced. Therefore, it can be easily mixed or blended without a solvent. Fine powder.

Examples of epoxy resins using amines as precursors include the respective positions of tetraglycidyl diamino diphenylmethane, xylylene diamine glycidyl compound, triglycidyl amino phenol, or glycidyl aniline. Isomers or substituted with alkyl or halogen. Examples of commercially available products of tetraglycidyl diamino diphenylmethane include Sumiepoxy ELM434, (made by Sumitomo Chemical Co., Ltd.), Araldite MY720, MY721, MY9512, MY9612, MY9634, and MY9663 (made by Huntsman Advanced Materials) JER604 (Mitsubishi Chemical Corporation). Examples of commercially available triglycidylaminophenols include JER630 (manufactured by Mitsubishi Chemical Corporation), Araldite MY0500, MY0510 (manufactured by Huntsman Advanced Materials), and ELM100 (manufactured by Sumitomo Chemical Co., Ltd.). Examples of commercially available products of glycidyl anilines include GAN and GOT (manufactured by Nippon Kayaku Co., Ltd.).

In addition, as the curable resin composition of the present invention, if a fine powder such as fine cellulose fibers is mixed or blended to have a low viscosity, a decrease in heat resistance will be seen. In order to improve this phenomenon, if blended to make A component having improved heat resistance tends to have a higher viscosity, but the problem can be resolved by blending a bisphenol A epoxy resin and a bisphenol F epoxy resin together.

In addition, since alkyl glycidyl ether such as 1,6-hexanediol diglycidyl ether has a low viscosity, when the viscosity of the composition is high, it is desirable to use it as a diluent or viscosity adjustment.

In the present invention, as the thermosetting component (B), a thermosetting resin other than a cyclic ether compound may be used as desired. As the thermosetting resin other than the cyclic ether compound, any resin may be used as long as it is hardened by heating. Examples include varnish-type phenol resins such as novolac resin, cresol varnish resin, and bisphenol A varnish resin. Phenolic resins such as phenolic resins, phenol resins modified with tung oil, linseed oil, walnut oil, and other phenolic resins such as phenolic resins, phenoxy resins, urea, etc. (urea) Triazine ring-containing resins such as resins, melamine resins, unsaturated polyester resins, bismaleimide resins, diallyl phthalate resins, siloxane resins, Resin of azine ring, original norbornene resin, cyanate resin, isocyanate resin, urethane resin, benzocyclobutene resin, maleimide resin, bismaleimide triazine resin, Polyazomethyl resin, thermosetting polyfluorene imine, dicyclopentadienyl diphenol ester compound, bisphenol A diacetate, diphenyl phthalate, diphenyl terephthalate, p- Active esters of bis [4- (methoxycarbonyl) phenyl] phthalate Wait.

(B) The blending amount of the thermosetting component is preferably 10 to 70% by mass based on the total amount of the composition. When it is 10% by mass or more, workability such as printing is excellent. If it is 70% by mass or less, the thermal expansion will be lower. Still more preferably, it is 20 to 60% by mass.

[Hardener] The hardening resin composition of the present invention is preferably used as a hardener. As the hardener of the present invention, for example, an imidazole compound can be used. Examples of the imidazole compound include 2-methylimidazole, 4-methyl-2-ethylimidazole, 2-phenylimidazole, 4-methyl-2-phenylimidazole, and 1-benzyl-2-methyl. Imidazole, 2-ethylimidazole, 2-isopropylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl- 2-Undecyl imidazole and other imidazole derivatives.

Examples of the imidazole compound include an imidazole compound having a triazine structure. Examples of the imidazole compound including a triazine structure include 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-S-triazine, and 2,4-diamine. Amino-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 Wait. Examples of such commercially available products include 2MZ-A, 2MZ-AP, 2MZA-PW, C11Z-A, and 2E4MZ-A (Shikoku Chemical Industries, Ltd.).

Among 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 hardening resin composition is excellent in storage stability, and a hardened material that does not crack due to short-term hardening can be obtained.

As the hardener, compounds other than imidazole compounds can also be used. For example, dicyandiamine and its derivatives, melamine and its derivatives, diaminomalononitrile and its derivatives, diethylene glycol, triethylene glycol Ethylenetetramine, tetramethylenepentamine, bis (hexamethylene) triamine, triethanolamine, diaminodiphenylmethane, benzyldimethylamine, 4- (dimethylamino) -N, N -Dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, dihydrazine adipate, sebacic acid Organic hydrazine and other amines such as dihydrazine, 1,8-diazabicyclo [5.4.0] undecene-7, 3,9-bis (3-aminopropyl) -2,4 , 8,10-tetraspiro [5.5] undecane, or organic phosphine compounds such as triphenylphosphine, tricyclohexylphosphine, tributylphosphine, methyldiphenylphosphine, phenol compounds, etc. In addition, as commercially available products, there are, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (Shikoku Chemical Industry Co., Ltd.), ATU (Ajinomoto (Co.)), U-CAT3503N, U -CAT3502T, DBU, DBN, U-CATSA102, U-CAT5002 (San Apro). Familiar with dicyandiamine, melamine, or acetoguanamine, benzoguanamine, 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl Radical] -2,4,8,10-tetraspirocyclo [5.5] undecane and other guanidine amines and derivatives thereof, and organic acid salts or epoxy adducts thereof have adhesion to copper Or the rust-proof property can not only function as a hardener for epoxy resins, but also contribute to the prevention of copper discoloration of printed wiring boards.

As the phenol compound, for example, a phenol novolak resin, an alkyl novolak resin, a varnish resin containing a triazine structure, a bisphenol A varnish resin, a dicyclopentadiene type phenol resin, and a Zyloric type phenol can be used alone or in combination. Resins, Copna resins, terpene modified phenol resins, phenol compounds such as polyvinyl phenols, naphthalene-based hardeners, and fluorene-based hardeners are known and commonly used. Examples of the phenol compounds include HE-610C, 620C manufactured by Air Water, and TD-2131, TD-2106, TD-2093, TD-2091, TD-2090, and VH-4150 made by DIC (stock). , VH-4170, KH-6021, KA-1160, KA-1163, KA-1165, TD-2093-60M, TD-2090-60M, LF-6161, LF-4871, LA-7052, LA-7054, LA -7751, LA-1356, LA-3018-50P, EXB-9854, SN-170, SN180, SN190, SN475, SN485, SN495, SN375, SN395, JX Nippon Steel & Nippon Stone Energy DPP, Meiwa Chemicals HF-1M, HF-3M, HF-4M, H-4, DL-92, MEH-7500, MEH-7600-4H, MEH-7800, MEH -7851, MEH-7851-4H, MEH-8000H, MEH-8005, XL, XLC, RN, RS, RX, etc. manufactured by Mitsui Chemicals Co., Ltd., but not limited to these.

The hardener may be used alone or in combination of two or more. The blending amount of the curing agent may be a known and commonly used blending amount with respect to the thermosetting component. For example, it is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the epoxy resin. However, when the hardener is a phenol compound, it is preferably 1 to 150 parts by mass based on 100 parts by mass of the epoxy resin.

[(C) Borate Compound] 硬化 The curable resin composition of the present invention can contain a borate compound. The borate compound has the effect of improving the storage stability of the resin composition, so it is more desirable to use it. The borate compound reacts with the surface of the latent hardening accelerator to modify the surface of the latent hardening agent and encapsulates the surface. Examples of the borate compound include trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, and tri-n-butyl borate , Tri-n-pentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate , Docosyl borate, hexadecyl borate, octadecyl borate, ginseng (2-ethylhexyloxy) borane, bis (1,4,7,10-tetraoxy (Heteroundecyl) (1,4,7,10,13-pentaoxatetradecyl) (1,4,7-trioxaundecyl) borane, tribenzylborate, triphenyl Borates, tri-o-tolyl borate, tri-m-tolyl borate, triethanolamine borate, and the like. These can be purchased as test drugs. In addition, as commercially available products, there are Cureduct L-07N and L-07E (manufactured by Shikoku Chemical Industry Co., Ltd.) which are blended products of epoxy resin and novolac resin.

A borate compound may be used individually by 1 type, and may be used in combination of 2 or more type. The blending amount of the borate compound is preferably 0.01 to 3 parts by mass relative to 100 parts by mass of the thermosetting component. When it is 0.01 parts by mass or more, storage stability is good. When it is 3 parts by mass or less, the curability is good.

[(D) Filler] 硬化 The curable resin composition of the present invention can further contain a filler other than the fine powder (A). As fillers other than the aforementioned (A) fine powder, in accordance with the required characteristics of the curable resin composition of the present invention, as long as they are appropriately known, organic fillers and inorganic fillers can be used, but inorganic fillers are more preferred. Examples of the inorganic filler include barium sulfate, barium titanate, amorphous silica, crystalline silica, molten silica, spherical silica, talc, white clay, magnesium carbonate, calcium carbonate, alumina, Aluminum hydroxide, mica powder, diatomaceous earth, silicon nitride, aluminum nitride, etc. Among the inorganic fillers, calcium carbonate is preferred.

The shape of the filler includes a spherical shape, a needle shape, a plate shape, a scale shape, a hollow shape, an irregular shape, a hexagonal shape, a cubic shape, a flake shape, and the like, but a spherical shape is preferable from the viewpoint of high filling properties.

The filler may be used singly or in combination of two or more kinds. The blending amount of the filler is preferably 10 to 70% by mass, and more preferably 20 to 60% by mass relative to the entire amount of the composition. When it is 10% by mass or more, workability such as printing is excellent. When it is 70% by mass or less, the thermal expansion becomes lower.

[Other Ingredients] 有机 In the curable resin composition of the present invention, it is not necessary to use an organic solvent, but for the purpose of adjusting the viscosity of the composition, etc., an organic solvent may be added to the extent that pores are not generated.

Furthermore, the curable resin composition of the present invention can be blended with titanium cyanine blue, titanium cyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc. as necessary. Well-known and commonly used coloring agents can be blended with well-known and commonly used heat-resistant materials such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, gallophenol, phenothiazine, etc. in order to provide stability during storage. Polymerization agents, white clay, kaolin clay, organic bentonite, montmorillonite and other well-known and commonly used thickeners or thixotropic agents, defoamers and / or leveling agents such as silicone, fluorine, and polymer, imidazole, Well-known and conventional additives such as adhesion-imparting agents such as thiazole-based, triazole-based, and silane coupling agents, photopolymerization initiators, dispersants, and flame retardants.

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

The curable resin composition of the present invention obtained as described above can be easily filled in through holes or through holes of a printed wiring board by a conventional method such as a screen printing method, a roll coating method, or a die coating method. Hole.

Therefore, the viscosity of the curable resin composition of the present invention is in the range of 100 to 1000 dPa · s at 25 ± 1 ° C, and further preferably 200 to 900 dPa · s, especially 300 to 800 dPa · s. By setting it in such a range, filling of a hole part is easy, and a hole etc. can be filled in a recessed part or a through hole well.

The glass transition temperature (Tg) of the curable resin composition of the present invention is preferably 150 ° C or higher, and more preferably 160 ° C or higher. When Tg is 150 ° C or higher, peeling (delamination) can be suppressed.

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

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

Hereinafter, the curable resin composition of the present invention is filled in a recess or a through hole such as a through hole or a through hole provided on a wiring board, and a printed wiring board on which a solder pad or wiring is formed above will be described with reference to FIG. 7-1. An example of a manufacturing method.

(1) Buried hole First, as shown in FIG. 7-1 (a), a through-hole 103 is formed on a wiring substrate 101 having a through-hole 103 and a conductor circuit layer 104 on a substrate 102 (multilayer printing is used as a core substrate) In the case of a wiring board, it is a recessed portion such as a through hole other than the through hole), and the through hole 103 is filled with the curable resin composition of the present invention as shown in FIG. 7-1 (b). For example, a photomask having an opening provided in a through-hole portion is mounted on a substrate, and filled in the through-hole by a printing method, a halftone printing method, or the like. Here, as the wiring substrate 101, a glass epoxy substrate, a polyimide resin substrate, a bismaleimide-triazine resin substrate, and a fluororesin substrate were bonded to a copper foil by a drill. Resin substrates, ceramic substrates, metal substrates, and other substrates 102 can be used appropriately by cutting through-holes and applying electroless plating or further electrolytic plating to the wall surface of the through-holes and the surface of the copper foil. The through-hole 103 and the conductor circuit layer 104 are formed. Copper plating is generally used as the plating.

(2) Grinding Next, the filled curable resin composition is heated at about 90 to 130 ° C. for about 30 to 90 minutes to prepare it for hardening. The hardness of the pre-hardened hardened material 105 is relatively low in this way, and therefore, unnecessary portions that can seep out of the surface of the substrate can be easily removed by physical polishing, and the flat surface can be made. After that, the hardening (complete hardening) is performed by heating again at about 140 to 180 ° C for about 30 to 90 minutes. In addition, the "pre-curing" or "pre-curing" as used herein generally means a state in which the reaction rate of epoxy is 80% to 97%. The hardness of the preliminary hardened material can be controlled by changing the heating time and heating temperature of the preliminary hardening. After that, as shown in FIG. 7-1 (c), unnecessary portions of the hardened body 105 that have leaked out of the through-holes are removed and flattened by grinding. The honing can be performed by a belt sander, polishing, or the like.

(3) Formation of the conductor circuit layer As shown in Figure 7-1 (d), a plated film is formed on the surface of the substrate where the through hole is buried. After that, an etching photoresist is formed, and a non-photoresist-forming portion is etched (not shown). Next, by stripping the etching resist, as shown in FIG. 7-1 (e), a conductive circuit layer 106 is formed.

As described above, the curable resin composition of the present invention can be suitably used as a resin filler for through holes provided in a printed wiring board as shown in FIG. 7-1, and further suitable as shown in FIG. 7-2 or FIG. 7-3. The resin fillers shown in the through-holes or through-holes provided in the multilayer printed wiring board are used, but they are not limited to these applications, and can also be used in applications such as sealing materials. Examples

Hereinafter, the present invention will be described in more detail by using examples. <First Example> [Preparation of fibrous fine cellulose powder] Production Example 1 (CNF1) 针 Coniferous bleached kraft pulp fibers (Machenzie CSF650ml, manufactured by Fletcher Challenge Canada) were thoroughly stirred with 9900 g of ion-exchanged water. Tempo (2,2,6,6-tetramethylpiperidine 1-oxy radical produced by ALDRICH), 12.5 mass% sodium bromide, and 28.4% by mass of sodium hypochlorite. Using pH-stat, 0.5 M sodium hydroxide was dropped and the pH was maintained at 10.5. After the reaction was performed for 120 minutes (20 ° C), the dropping of sodium hydroxide was stopped to obtain an oxidized slurry.充分 Wash the obtained oxidized slurry with ion-exchanged water, and then perform dehydration treatment. Thereafter, 3.9 g of the oxidized slurry and 296.1 g of ion-exchanged water were subjected to a refining treatment twice at 245 MPa using a high-pressure homogenizer (manufactured by Sugino machine, Starburst Lab HJP-2 5005) to obtain a fine cellulose powder containing a carboxyl group. Dispersion (solid content concentration: 1.3% by mass).

Next, 4087.75 g of the obtained carboxyl group-containing fine cellulose powder dispersion was placed in a beaker, and 4085 g of ion-exchanged water was added as a 0.5% by mass aqueous solution, followed by stirring at room temperature (25 ° C.) with a mechanical stirrer for 30 minutes. Next, 245 g of a 1 M aqueous hydrochloric acid solution was added, and reacted at room temperature for 1 hour. After completion of the reaction, it was reprecipitated with acetone and filtered, and then washed with acetone / ion-exchanged water to remove hydrochloric acid and salts. Finally, acetone was added and filtered to obtain a dispersion liquid (solid content concentration: 5.0% by mass) of the acetone-containing acid type cellulose powder in a state where the carboxyl group-containing fine cellulose powder was swelled in acetone. After completion of the reaction, the mixture was filtered, and then washed with ion-exchanged water to remove hydrochloric acid and salts. After solvent substitution with acetone, solvent substitution with DMF, a dispersion of acid-type cellulose powder containing DMF with a carboxyl-containing fine cellulose powder in an expanded state (average fiber diameter of 3.3 nm, solid content concentration) was obtained. 5.0% by mass).

Production Example 2 (CNF2) 40 40 g of the dispersion liquid of the DMF-containing acidic cellulose powder obtained in Production Example 1 and 0.3 g of hexylamine were placed in a beaker equipped with an electromagnetic stirrer and a stirrer, and 300 g of ethanol was used to dissolve the solution. The reaction solution was allowed to react at room temperature (25 ° C) for 6 hours. After completion of the reaction, filtration was performed, and washing with DMF and solvent substitution were performed to obtain a fine cellulose powder (a solid content concentration of 5.0% by mass) of a fine cellulose powder having an amine bonded to the amine via an ion bond. CNThe CNF2 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.

Production Example 3 (CNF3) 纤维 Fibrous fine cellulose powder (BiNFi-s manufactured by Sugino Machine, average fiber diameter 80 nm) was dehydrated and filtered, and carbitol acetate was added at 10 times the mass of the filter material. After stirring for 30 minutes, it was filtered. The replacement operation was repeated three times, and carbitol acetate was added in an amount of 20 times the mass of the filter material to prepare a dispersion liquid of fine cellulose powder (solid content concentration: 5.0% by mass).

[Preparation of cellulose nanocrystalline particles] Manufacturing Example 4 (CNC1) The dried coniferous dried kraft pulp slurry was processed with a coarse grinder and a pin mill to become cotton fibers. This cotton-like fiber was taken out with an absolute dry mass of 100 g, suspended in 2 L of a 64% sulfuric acid aqueous solution, and hydrolyzed at 45 ° C. for 45 minutes.

The suspension liquid thus obtained was filtered, and 10 L of ion-exchanged water was poured therein, and after stirring, they were uniformly dispersed to obtain a dispersion liquid. Next, this dispersion was subjected to a filtration and dehydration step and repeated three times to obtain a dehydrated sheet. Next, the obtained dehydrated flakes were diluted with 10 L of ion-exchanged water, and a 1N sodium hydroxide aqueous solution was added a little at a time while stirring, and the pH was set to about 12. After that, the suspension was filtered and dehydrated, 10 L of ion-exchanged water was added, and the filtration and dehydration step was repeated after stirring.

Next, ion exchanged water was added to the obtained dehydrated sheet to prepare a 2% suspension. This suspension was passed through a wet micronization device ("Ultimaizer" by Sugino Machine Co., Ltd.) at a pressure of 245 MPa for 10 times to obtain an aqueous dispersion of cellulose nanocrystal particles.

Then, after solvent substitution with acetone, solvent substitution with DMF, a DMF dispersion liquid (solid content concentration 5.0% by mass) in which the cellulose nanocrystal particles were in an expanded state was obtained. As a result of measuring the cellulose nanocrystal particles in the obtained dispersion liquid by AFM observation, the average crystal width was 10 nm, and the average crystal length was 200 nm.

Production Example 5 (CNC2) Aside from changing the cellulose raw material in Production Example 4 to absorbent cotton (manufactured by White Cross), the same method was used to obtain a DMF dispersion (solid form) in which cellulose nanocrystalline particles were in an expanded state. Sub-concentration 5.0% by mass). As a result of measuring cellulose nanocrystal particles in the obtained dispersion liquid by AFM observation, 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 the ingredients according to the descriptions in Tables 1 to 3 below, a high-pressure homogenizer Nanovater manufactured by Yoshida Machinery Industries was used. NVL-ES008 was repeated 6 times to disperse, and each composition was prepared. The numerical values in Tables 1 to 3 represent parts by mass. About each composition obtained by the Example and the comparative example, the thermal expansion coefficient, solder heat resistance, insulation, and toughness (tensile rate) were evaluated. The evaluation method is as follows.

[Coefficient of Thermal Expansion] 涂布 Apply each composition on a PET film with a thickness of 38 μm using an applicator with a pitch of 120 μm, and dry it at 90 ° C. for 10 minutes in a hot-air circulation drying furnace to obtain a dry film with a resin layer of each composition. Thereafter, a copper foil having a thickness of 18 μm was pressed with a vacuum laminator at 60 ° C. and a pressure of 0.5 MPa for 60 seconds, and the resin layers of the respective compositions were laminated to peel off the PET film. Next, it was heated at 180 ° C. for 30 minutes in a hot-air circulation drying furnace to harden it, and was peeled from the copper foil to obtain a thin film sample made of the hardened material of each composition. The obtained film sample was cut into a length of 3 mm × 30 mm as a test piece for measuring the thermal expansion coefficient. About this test piece, TMA (Thermome Mechanical Analysis) Q400 manufactured by TA Instrument was used, the chuck pitch was 16 mm in a tensile mode, and a load of 30 mN was heated to 20 to 250 ° C. at 5 ° C./min in a nitrogen environment, and then at 5 ° C. The temperature is reduced to 250 ~ 20 ° C / min, and the thermal expansion coefficients α1 and α2 (ppm / K) are measured. These measurement results are combined and shown in Tables 1-3.

[Solder heat resistance] Apply on a FR-4 copper-laminated laminated board with a size of 150mm × 95mm and a thickness of 1.6mm, and apply the entire composition with 80 mesh Tedlon regular twill pattern screen printing, and dry it in hot air circulation The furnace was dried at 80 ° C. for 30 minutes, and then heated and cured at 180 ° C. for 30 minutes to obtain a test substrate of a resin layer formed of a cured product of each composition. A rosin-based flux was applied to the surface of the resin layer of this test substrate, and the solder layer flowing at 260 ° C for 60 seconds was washed with propylene glycol monomethyl ether acetate, and then washed with ethanol. Regarding the test substrate after cleaning, the swelling or peeling of the resin layer and changes in the surface state were visually observed to evaluate solder heat resistance. The evaluation criteria were set to be X when abnormality in the resin layer was observed, such as swelling or peeling, and surface dissolution or softening, and ○ when no observation was observed. The evaluation results are combined and shown in Tables 1-3.

[Insulation] Apply each composition on a PET film with a thickness of 38 μm using an applicator with a pitch of 120 μm, and dry it at 90 ° C. for 10 minutes in a hot air circulation drying oven to obtain a dry film with a resin layer of each composition. Thereafter, a test piece of IPC MULTI-PURPOSE TEST BOARD B-25 of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm-thick FR-4 substrate with a copper thickness of 35 μm was pressed on a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds. Second, the resin layer of each composition was bonded, the PET film was peeled off, and it was heated at 180 ° C. for 30 minutes in a hot-air circulation drying furnace to harden it. Next, cut off the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 as an electrically independent terminal (cut by the dotted line in Figure 1-4). Then, a bias of 500 VDC was applied to the upper part of the A test piece as the cathode and the lower part as the anode, and the insulation resistance value was measured and evaluated. The evaluation criterion is set to ○ if the insulation resistance value is 100 GΩ or more, and × when the insulation resistance value is less than 100 GΩ. The evaluation results are combined and shown in Tables 1-3.

[Toughness] Apply each composition on a PET film with a thickness of 38 μm with an applicator with a pitch of 200 μm, and dry it in a hot air circulation drying oven at 90 ° C. for 20 minutes to obtain a dry film with a resin layer of each composition. Next, an electrolytic copper foil with a thickness of 18 μm and a glossy side facing upward was fixed on a FR-4 copper-laminated laminate with a thickness of 1.6 mm with a tape, and the dry film was vacuum-bonded with a 60 ° C. pressure 0.5 MPa. The resin layer of each composition was laminated on the electrolytic copper foil under pressure for 60 seconds under conditions, and then the PET film was peeled off and heated at 180 ° C. for 30 minutes in a hot-air circulation drying furnace to harden the resin layer. Then, the fixed tape was peeled, and the electrolytic copper foil was further peeled to obtain a thin film sample made of a resin layer. Next, the above-mentioned film sample was cut to a specific size in accordance with JIS K7127 to prepare a test piece for evaluation. For this test piece, a small table tester EZ-SX manufactured by Shimadzu Corporation was used to measure the stress [MPa] and skew [%] at a pulling speed of 10 mm / min. The skewness [%] at this time is the elongation at the time of breaking the test piece. The larger the toughness, the higher the toughness evaluation. Therefore, the skewness [%] is used to evaluate the toughness. The evaluation criterion is that the skewness [%] is less than 2.0% and is set to ×, and the 2.0% or more is set to 0. The evaluation results are combined and shown in Tables 1-3.

* 1-1) Thermosetting resin 1-1: Epiclon HP-4032 DIC (stock) Cyclohexanone varnish (cyclic ether compound with naphthalene skeleton) made of 50% by mass solids * 1-2) thermosetting Resin 1-2: NC-7300L Cyclohexanone varnish (cyclic ether compound with naphthalene skeleton) made of 50% by mass of Nippon Kayaku Co., Ltd. 1-3 * 1-3) Thermosetting resin 1-3: YX- 8800 Cyclohexanone varnish (cyclic ether compound with onion skeleton) made by Mitsubishi Chemical Corporation (50% by mass) 1-4 * 1-4) thermosetting resin 1-4: Epiclon HP-7200 solid content by 50% by mass Cyclohexanone varnish (cyclic ether compound with dicyclopentadiene skeleton) 1-5 * 1-5) Thermosetting resin 1-5: NC-3000H 50% by mass of cyclohexanone made by Nippon Kayaku Co., Ltd. Varnish (Cyclic ether compound with biphenyl skeleton) 1-6 * 1-6) Thermosetting resin 1-6: YX-4000 Cyclohexanone varnish (solid biphenyl skeleton) Cyclic ether compound) * 1-7) Thermosetting resin 1-7: Cyclohexanone varnish * 1-8) of Epiclon N-740 DIC (solid) solid content of 50% by mass) Thermosetting resin 1-8: Epiclon 830 DIC (shares) system * 1-9) Thermosetting resin 1-9: JER827 made by Mitsubishi Chemical Corporation * 1-10) Phenoxy resin 1-1: YX6954 30% by mass of cyclohexanone varnish made by Mitsubishi Chemical Corporation * 1-11) Hardener 1-1: HF-1 60% by mass of cyclohexanone varnish * 1-12 manufactured by Meiwa Chemicals Co., Ltd. Hardener 1-2: Bisphenol A diacetate Stock) (active ester) * 1-13) hardening catalyst 1-1: 2E4MZ (2-ethyl-4-methylimidazole) Shikoku Chemical Industry (stock) * 1-14) filler 1-1: Adma Fine SO-C2 (share) Admatechs (silica dioxide) * 1-15) Organic solvent 1-1: dimethylformamide * 1-16) Antifoaming agent 1-1: BYK-352 Big Chemie Japan (Share) system

* 1-17) Filler 1-2: B-30 Barium sulfate made by Sakai Chemical Industry Co., Ltd. * 1-18) Filler 1-3: DAW-07 Denka (stock) Alumina * 1-19) Dispersant 1 -1: DISPERBYK-111 manufactured by Big Chemie

From the results described in Tables 1 to 3, it is clearly confirmed that by using a filler other than the fine cellulose fibrous substance and the fine cellulose fibrous substance together, it is possible to obtain a low temperature not only at normal temperature but also in a high-temperature region during component mounting. It is a hardened product with excellent thermal expansion coefficient and toughness. In addition, from the results of the evaluation of the solder heat resistance, it was confirmed that the compositions of the examples are excellent in heat resistance or chemical resistance, and can be used as a composition for wiring boards. Furthermore, it was confirmed that the relative permittivity and loss factor can be reduced by using an active ester as a hardener.

<Second Example> As the fine cellulose fibers CNF1 to CNF3 and cellulose nanocrystal particles CNC1 and CNC2, the same manufacturing examples 1 to 5 as in the first embodiment were used.

Synthesis example 1 (varnish 1) 900 g of diethylene glycol dimethyl ether as a solvent was added to a 2-liter separation type measuring flask equipped with a stirrer, a thermometer, a reflow cooler, a dropping funnel, and a nitrogen introduction tube, and as a polymerization start 21.4 g of t-butylperoxy 2-ethylhexanoate (manufactured by Nippon Oil Co., Ltd .; trade name; Perbutyl O) was heated to 90 ° C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and lactone modified 2-hydroxyethyl methacrylate (made by Daicel, trade name; Placcel FM1) were 109.8 g. 21.4 g of bis (4-t-butylcyclohexyl) peroxydicarbonate (produced by Nippon Oil Co., Ltd .; trade name; Peroyl TCP) and a polymerization initiator were added dropwise within 3 hours at the same time. Furthermore, this was aged for 6 hours to obtain a carboxyl group-containing copolymer resin. Moreover, these reactions are performed under a nitrogen environment.

Next, 363.9 g of 3,4-epoxycyclohexyl methacrylate (made by Daicel, trade name; Cyclomer A200) was added to the obtained carboxyl-containing copolymerized resin as dimethyl ring-opening catalyst. 3.6 g of benzylamine and 1.80 g of hydroquinone monomethyl ether as a polymerization inhibitor were heated to 100 ° C, and the ring-opening addition reaction of epoxy was carried out by stirring this. After 16 hours, a solution containing 53.8% by mass (non-volatile 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): A diethylene glycol monoethyl ether acetate as a solvent and azobisisobutyronitrile as a catalyst were added to a measuring bottle equipped with a thermometer, a stirrer, a dropping funnel, and a reflux cooler. In a nitrogen environment, this is heated to 80 ° C., and the monomer mixed with methacrylic acid and methmethacrylate at a molar ratio of 0.40: 0.60 is dropped within about 2 hours. After further stirring this for 1 hour, the temperature was raised to 115 ° C. and deactivated to obtain a resin solution.

After cooling the resin solution, using this as a catalyst, tetrabutylammonium bromide was used at a temperature of 95-105 ° C for 30 hours to make butyl glycidyl ether at a molar ratio of 0.40 to that of the obtained resin. The carboxyl groups are subjected to addition reaction in an equal amount to cool. Further, the OH group of the resin obtained above was subjected to an addition reaction with tetrahydrophthalic anhydride at a molar ratio of 0.26 under the conditions of 95 to 105 ° C. for 8 hours. This was taken out after cooling, and a solution containing 50% by mass (non-volatile matter) of a carboxyl group-containing resin having an acid value of 78.1 mgKOH / g and a mass average molecular weight of 35,000 was obtained.

Synthesis Example 3 (Varnish 3) 210 g of a cresol varnish-type epoxy resin (manufactured by DIC (Epiclon), Epiclon N-680, epoxy equivalent weight = 210) was added to a measuring bottle equipped with a thermometer, a stirrer, a dropping funnel, and a reflux cooler. 96.4 g of carbitol acetate as a solvent was 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 here. This mixture was heated to 95-105 degreeC, and 72 g of acrylic acid was dripped gradually until the acid value became 3.0 mgKOH / g or less, and it was made to react for about 16 hours. After cooling the reaction product to 80 to 90 ° C, 76.1 g of tetrahydrophthalic anhydride was added, and the reaction was allowed to proceed for about 6 hours until the absorption peak (1780 cm-1) of the acid anhydride disappeared by infrared absorption analysis. To this reaction solution, 96.4 g of Ipuzoru # 150, an aromatic solvent made by Idemitsu Kosan Co., Ltd., was added, and the diluted solution was taken out. The carboxyl group-containing photosensitive polymer solution thus obtained had a non-volatile content of 65% by mass and a solid content acid value of 78 mgKOH / g.

After mixing the components according to the descriptions in Tables 4 to 12 below, a high-pressure homogenizer Nanovater NVL-ES008 manufactured by Yoshida Machinery Industrial Co., Ltd. was used 6 times to disperse and prepare each composition. The numerical values in Tables 4 to 12 represent parts by mass.

[Interlayer insulation reliability] (Thermosetting composition) On a PET film with a thickness of 38 μm, each composition shown in Tables 4 to 6 was applied with an applicator with a pitch of 120 μm, and it was heated in a hot-air circulation type drying furnace at 90 ° C. It dried for 10 minutes, and obtained the dry film of the resin layer which has each composition. Then, on the A test piece of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6mm-thick FR-4 substrate with a copper thickness of 35μm (the part shown by the arrow in Figure 2-2: (Right) A vacuum laminator is pressed for 60 seconds under the conditions of 60 ° C and a pressure of 0.5 MPa. The resin layers of each composition are laminated, the PET film is peeled off, and it is heated at 180 ° C for 30 minutes in a hot air circulation drying furnace to harden . Next, the treatment was performed in the order of permanganic acid decontamination (manufactured by ATOTECH), electroless copper plating (Thru-Cup PEA, manufactured by Uemura Industry Co., Ltd.), and electrolytic copper plating treatment, and copper plating with a copper thickness of 25 μm was applied. Applied treatment. Next, a tempering treatment was performed in a hot-air circulation-type drying furnace at 190 ° C for 60 minutes to obtain a test substrate to which a copper plating treatment was applied. Then, an acid-resistant tape formed into a circle having a diameter of 1 cm was placed on the center of the test piece A to be adhered to the copper plating, and the acid-resistant tape portion on the resin hardened product was cured at 40 ° C with a 40% by mass solution of a second iron solution. The other copper plating is removed by etching. At this time, the test substrate was formed on a test piece of IPC MULTI-PURPOSE TEST BOARD B-25, and the hardened material of each composition was formed as a coating film, and a circular copper plating with a diameter of 1 cm was formed above it. (Refer to Figure 2-3). Next, wire was mounted on the round copper plated with rhenium solder and soldering iron, and the wires were similarly mounted on the wiring of the IPC MULTI-PURPOSE TEST BOARD. The round was used as the anode, and the wiring was used as the cathode. The voltage was tested at 130 ° C and 85% for 200 hours. Ten test pieces were prepared from each composition. At this time, when the insulation resistance was measured, it was NG when it was 1 × 10 ⁶ Ω or less. All those without NG until the end of the test were evaluated as ◎, those with 1 to 4 NG were evaluated as ○, those with 5 to 9 NG were evaluated as △, and those who were all NG were evaluated as ×. The evaluation results are shown in Tables 4 to 6.

(Photocurable thermosetting composition) Each composition shown in Tables 7 to 12 was coated on a PET film having a thickness of 38 μm with an applicator having a pitch of 120 μm, and dried in a hot-air circulation type drying oven at 90 ° C. for 10 minutes. To obtain a dry film of a resin layer having each composition. Thereafter, a test piece of IPC MULTI-PURPOSE TEST BOARD B-25 of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm-thick FR-4 substrate with a copper thickness of 35 μm was pressed on a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds. In seconds, the resin layers of each composition were bonded, and the metal film was exposed at 700 mJ / cm ² by a metal halide lamp exposure machine for a printed wiring board. After that, the PET film was peeled off, and 1% by weight of Na ₂ CO ₃ at 30 ° C was used. The developing solution is developed by a developing machine for 60 seconds. Then, it heated at 150 degreeC for 60 minutes in the hot-air circulation type drying furnace, and hardened. Next, the treatment was performed in the order of permanganic acid decontamination (manufactured by ATOTECH), electroless copper plating (Thru-Cup PEA, manufactured by Uemura Industrial Co., Ltd.), and electrolytic copper plating treatment, and copper plating with a thickness of 25 μm was applied. Applied treatment. Next, a tempering treatment was performed in a hot-air circulation-type drying furnace at 190 ° C for 60 minutes to obtain a test substrate to which a copper plating treatment was applied. Then, an acid-resistant tape formed into a circle having a diameter of 1 cm was placed on the center of the test piece A to be adhered to the copper plating, and the acid-resistant tape portion on the resin hardened product was cured at 40 ° C with a 40% by mass solution of a second iron solution. The other copper plating is removed by etching. Next, wire was mounted on the round copper plated with rhenium solder and soldering iron. The wires were similarly mounted on the wiring of the IPC MULTI-PURPOSE TEST BOARD. The round was used as the anode and the wiring was used as the cathode. The voltage was tested at 130 ° C and 85% for 200 hours. Ten test pieces were prepared from each composition. At this time, when the insulation resistance was measured, it was NG when it was 1 × 10 ⁶ Ω or less. All those without NG until the end of the test were evaluated as ◎, those with 1 to 4 NG were evaluated as ○, those with 5 to 9 NG were evaluated as △, and those who were all NG were evaluated as ×. The evaluation results are shown in Tables 7 to 12.

[Comb Electrode Insulation Reliability] (Thermosetting composition) On a PET film with a thickness of 38 μm, each composition shown in Tables 4 to 6 was coated with an applicator with a pitch of 120 μm, and then heated in a hot-air circulation drying oven at 90 ° C. This was dried for 10 minutes to obtain a dry film of a resin layer having each composition. Thereafter, a test piece of IPC MULTI-PURPOSE TEST BOARD B-25 of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm-thick FR-4 substrate with a copper thickness of 35 μm was pressed on a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds. Second, the resin layer of each composition was bonded, the PET film was peeled off, and it was heated at 180 ° C. for 30 minutes in a hot-air circulation drying furnace to harden it. Next, cut off the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 as an electrically independent terminal (cut by the dotted line in Figure 2-4). In addition, a test was performed with a voltage of 50 V on the upper part of the A test piece as the cathode and the lower part as the anode, and the test was performed at 130 ° C and 85% for 200 hours. Ten test pieces were prepared from each composition. At this time, when the insulation resistance was measured, it was NG when it was 1 × 10 ⁶ Ω or less. All persons without NG until the end of the test were evaluated as 评价, 1 to 4 NG persons were evaluated as ○, 5 to 9 NG persons were evaluated as Δ, and all NG persons were evaluated as ×. The evaluation results are shown in Tables 4 to 6.

(Photocurable thermosetting composition) Each composition shown in Tables 7 to 12 was coated on a PET film having a thickness of 38 μm with an applicator having a pitch of 120 μm, and dried in a hot-air circulation type drying oven at 90 ° C. for 10 minutes. To obtain a dry film of a resin layer having each composition. Thereafter, a test piece of IPC MULTI-PURPOSE TEST BOARD B-25 of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm-thick FR-4 substrate with a copper thickness of 35 μm was pressed on a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds. In seconds, the resin layers of each composition were bonded, and the metal film was exposed at 700 mJ / cm ² by a metal halide lamp exposure machine for a printed wiring board. After that, the PET film was peeled off, and 1% by weight of Na ₂ CO ₃ at 30 ° C was used. The developing solution is developed by a developing machine for 60 seconds. Then, it heated at 150 degreeC for 60 minutes in the hot-air circulation type drying furnace, and hardened. Next, cut off the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 as an electrically independent terminal. In addition, a test was performed with the upper part of the A test piece as the cathode and the lower part as the anode, and a voltage of 50 V was applied at 130 ° C and 85% for 200 hours. Ten test pieces were prepared from each composition. At this time, when the insulation resistance was measured, it was NG when it was 1 × 10 ⁶ Ω or less. All those without NG until the end of the test were evaluated as ◎, those with 1 to 4 NG were evaluated as ○, those with 5 to 9 NG were evaluated as △, and those who were all NG were evaluated as ×. The evaluation results are shown in Tables 7 to 12.

[Solder heat resistance] (Thermosetting composition) The FR-4 copper-laminated laminated plate with a size of 150mm × 95mm and a thickness of 1.6mm is formed by printing each composition with a 80-mesh Tedlon dragon twill screen The overall stereo pattern was dried in a hot-air circulating drying oven at 80 ° C for 30 minutes, and then heated and hardened at 180 ° C for 30 minutes to obtain a test piece. A rosin-based flux was applied to the hardened material side of the composition of this test piece, and the solder layer flowing at 260 ° C for 60 seconds was washed with propylene glycol monomethyl ether acetate, and then washed with ethanol. About the test piece, the swelling or peeling of a coating film, and the change of a surface state were observed visually. Those who saw swelling or peeling of the coating film, and abnormalities such as dissolution or softening of the surface were evaluated as ×, and those who did not see it were evaluated as ○. The evaluation results are shown in Tables 4 to 6.

(Photo-curable thermosetting composition) On a 150mm × 95mm, 1.6mm thickness FR-4 copper-laminated laminated plate, each composition was printed on a 80-mesh Tedlon dragon twill pattern screen to form a comprehensive stereogram. Type, drying in a hot-air circulating drying furnace at 80 ° C for 30 minutes, and full exposure at 700 mJ / cm ² by a metal halide lamp exposure machine for printed wiring boards, using 1wt% Na ₂ CO ₃ at 30 ° C. The imaging liquid was developed on a developing machine for 60 seconds. Then, the test piece was obtained by heat-hardening at 150 degreeC for 60 minutes in the hot-air circulation type drying furnace. A rosin-based flux was applied to the hardened side of the composition of this test piece, and the solder layer flowing at 260 ° C for 60 seconds was washed with propylene glycol monomethyl ether acetate, and then washed with ethanol. The test piece was observed visually for swelling or peeling of the coating film, and for changes in the surface state. Those who saw swelling or peeling of the coating film, and abnormalities such as dissolution or softening of the surface were evaluated as ×, and those who did not see it were evaluated as ○. The evaluation results are shown in Tables 7 to 12.

[Production of a sample for measuring thermal expansion] (Thermosetting resin composition) Apply each composition shown in Tables 4 to 6 on a PET film with a thickness of 38 μm with an applicator with a pitch of 120 μm, and apply it to a hot air circulation drying oven at 90 ° C. It dried at 10 degreeC for 10 minutes, and obtained the dry film of the resin layer which has each composition. Thereafter, a copper foil having a thickness of 18 μm was pressed with a vacuum laminator at 60 ° C. and a pressure of 0.5 MPa for 60 seconds, and the resin layers of the respective compositions were laminated to peel off the PET film. Next, it was heated at 180 ° C. for 30 minutes in a hot-air circulation drying furnace to harden it, and the copper foil was peeled to obtain a sample of a cured film.

(Photocurable thermosetting resin composition) A copper foil with a thickness of 18 μm was attached to a FR-4 copper-clad laminate with a thickness of 1.6 mm, and each composition shown in Tables 7 to 12 was applied with an applicator with a pitch of 120 μm. , And dried in a hot air circulation type drying oven at 90 ° C for 10 minutes. After that, it was brought into close contact with a negative mask having a pattern of 3 mm width × 30 mm length, and exposed at 700 mJ / cm ² with a metal halide lamp exposure machine for a printed wiring board. Next, a developing solution of 1 wt% Na ₂ CO ₃ at 30 ° C. was used to develop for 60 seconds on a developing machine. Then, it heated at 150 degreeC in the hot-air circulation type drying furnace, and hardened for 60 minutes, and peeled the copper foil, and obtained the sample of a hardened film.

[Measurement of Thermal Expansion Ratio] (Thermosetting resin composition) 制作 The produced sample for thermal expansion measurement was cut into a width of 3 mm × length of 30 mm. TMA (Thermome Mechanical Analysis) Q400 manufactured by TA Instrument was used for this test piece, and the chuck pitch was 16 mm in a tensile mode, and a load of 30 mN was heated to 20 to 250 ° C. at 5 ° C./min in a nitrogen environment, and then 5 ° C./min. Measure the temperature by reducing the temperature to 250 ~ 20 ℃ in minutes. Calculate the average thermal expansion coefficient α1 from 30 ° C to 100 ° C and the average thermal expansion coefficient α2 from 200 ° C to 230 ° C when the temperature is lowered. The results are shown in Tables 4 to 6.

(Photocurable thermosetting resin composition) 进行 Except that the produced sample was used as it is, it was performed in the same manner as the thermosetting resin composition. The results are shown in Tables 7 to 12.

* 2-1) Thermosetting resin 2-1: Cyclohexanone varnish (cyclic ether compound with naphthalene skeleton) with a solid content of 50% by mass of Epiclon HP-4032 DIC (strand) * 2-2) Thermosetting Resin 2-2: NC-7300L Cyclohexanone varnish (cyclic ether compound with naphthalene skeleton) made of 50% by mass of Nippon Kayaku Co., Ltd. * 2-3) Thermosetting resin 2-3: YX- 8800 Cyclohexanone varnish (cyclic ether compound with onion skeleton) made by Mitsubishi Chemical Co., Ltd. with a solid content of 50% by mass * 2-4) thermosetting resin 2-4: solid made by Epiclon N-740 DIC (stock) 50% by mass of cyclohexanone varnish * 2-5) Thermosetting resin 2-5: Epiclon 830 DIC (Co.) * 2-6) Thermosetting resin 2-6: JER827 Mitsubishi Chemical Co., Ltd. * 2-7) Thermosetting resin 2-7: HF-1 60% by mass of cyclohexanone varnish made by Meiwa Kasei Co., Ltd. (2)) hardening catalyst 2-1: 2E4MZ (2-ethyl-4 -Methylimidazole) Shikoku Chemical Industry Co., Ltd. * 2-9) Filler 2-1: Adma Fine SO-C2 (Stock) Admatechs (Silicon Dioxide) * 2-10) Organic solvent 2-1: 2 Methylformamide * 2-11) Antifoaming agent 2-1: manufactured by BYK-352 Big Chemie Japan

* 2-18) Filler 2-2: B-30 Barium sulfate manufactured by Sakai Chemical Industry Co., Ltd. * 2-19) Filler 2-3: DAW-07 Denka (Alumina) manufactured by Denka * 2-20) Dispersant 2 -1: DISPERBYK-111 manufactured by Big Chemie

* 2-12) Hardening catalyst 2-2: Finely pulverized melamine Nissan Chemical Co., Ltd. * 2-13) Hardening catalyst 2-3: Dicyanodiamine * 2-14) Photopolymerization initiator 2 -1: Irgacure 907 BASF Co., Ltd. * 2-15) Photocurable resin 2-1: Dipentaerythritol tetraacrylate * 2-16) Thermosetting resin 2-8: TEPIC-H (Triglycidyl isocyanate) ) Nissan Chemical Co., Ltd. * 2-17) Colorant 2-1: Titanium Blue

From the results described in Tables 4 to 12, it was clearly confirmed that interlayer or electrode insulation can be obtained by including a fine powder such as fine cellulose fibers and a cyclic ether compound having at least one of a naphthalene skeleton and an onion skeleton. A curable resin composition having excellent reliability, especially insulation reliability between layers, and a low thermal expansion coefficient. In addition, from the results of the evaluation of the solder heat resistance, it was confirmed that the compositions of the examples are excellent in heat resistance or chemical resistance, and can be used as a composition for wiring boards.

<Third Example> As the fine cellulose fibers CNF1 to CNF3 and cellulose nanocrystalline particles CNC1 and CNC2, the same manufacturing examples 1 to 5 as in the first embodiment were used, and as the varnishes 1 to 3, the same as the first varnish 1 to 3 were used. The second embodiment is the same as the synthesis examples 1 to 3.

According to the descriptions in Tables 13 to 21 below, after mixing the components and stirring them, the high-pressure homogenizer Nanovater NVL-ES008 manufactured by Yoshida Machinery Industrial Co., Ltd. was repeated 6 times to disperse and prepare each composition. The numerical values in Tables 13 to 21 represent parts by mass.

[Peeling strength of plated copper] (Thermosetting composition) Apply on a PET film with a thickness of 38 μm, apply each composition shown in Tables 13 to 15 with an applicator with a pitch of 120 μm, and apply it in a hot air circulation drying oven at 90 ° C. This was dried for 10 minutes to obtain a dry film of a resin layer having each composition. Thereafter, a FR-4 copper-clad laminated board (copper thickness: 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm was pressed by a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds, and each was bonded. The resin layer of the composition was peeled off from the PET film and heated at 180 ° C. for 30 minutes in a hot-air circulation drying oven to harden it. Next, the treatment was performed in the order of permanganic acid decontamination (manufactured by ATOTECH), electroless copper plating (Thru-Cup PEA, manufactured by Uemura Industry Co., Ltd.), and electrolytic copper plating treatment, and copper plating with a copper thickness of 25 μm was applied. Applied treatment. Next, a tempering treatment was performed in a hot-air circulation-type drying furnace at 190 ° C for 60 minutes to obtain a test substrate to which a copper plating treatment was applied. The test substrate was cut to a width of 1 cm and a length of 7 cm or more. Using a small table tester EZ-SX manufactured by Shimadzu Corporation, a 90 ° printing peel mold was used to determine the peel strength at an angle of 90 degrees. In the evaluation, a value of 4.5 N / m or more was ○, a value of 2.5 N / m or more and less than 4.5 N / m was Δ, and a value of less than 2.5 N / m was x. The results are shown in Tables 13 to 15. In addition, if the peel strength is 4.5 N / m or more, it is considered that there is no problem of peeling even in a high-definition circuit. This benchmark is a very strict evaluation condition.

(Photocurable thermosetting composition) Each of the compositions shown in Tables 16 to 21 was coated on a PET film having a thickness of 38 μm with an applicator having a pitch of 120 μm, and dried in a hot air circulation drying oven at 90 ° C. for 10 minutes. To obtain a dry film of a resin layer having each composition. Thereafter, a FR-4 copper-clad laminated board (copper thickness: 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm was pressed by a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds, and each was bonded. The resin layer of the composition was subjected to full exposure at 700 mJ / cm ² with a metal halide lamp exposure machine using a printed wiring board, and then the PET film was peeled off, and a 1% by weight Na ₂ CO ₃ developing solution at 30 ° C. was used. The developing machine develops 60 seconds. Then, it heated at 150 degreeC for 60 minutes in the hot-air circulation type drying furnace, and hardened. Next, the treatment was performed in the order of permanganic acid decontamination (manufactured by ATOTECH), electroless copper plating (Thru-Cup PEA, manufactured by Uemura Industry Co., Ltd.), and electrolytic copper plating treatment, and copper plating with a copper thickness of 25 μm was applied. Applied treatment. Next, a tempering treatment was performed in a hot-air circulation-type drying furnace at 190 ° C for 60 minutes to obtain a test substrate to which a copper plating treatment was applied. The test substrate was cut to a width of 1 cm and a length of 7 cm or more. Using a small table tester EZ-SX manufactured by Shimadzu Corporation, a 90 ° printing peel mold was used to determine the peel strength at an angle of 90 degrees. In the evaluation, a value of 4.5 N / m or more was ○, a value of 2.5 N / m or more and less than 4.5 N / m was Δ, and a value of less than 2.5 N / m was x. The results are shown in Tables 16 to 21.

[Solder heat resistance] (Thermosetting composition) On a FR-4 copper-clad laminate with a size of 150 mm × 95 mm and a thickness of 1.6 mm, each composition shown in Tables 13 to 15 is obliquely tilted at 80 mesh The cloth pattern screen printing is used to form a comprehensive three-dimensional pattern, and it is dried in a hot air circulation drying oven at 80 ° C for 30 minutes, and then heated and hardened at 180 ° C for 30 minutes to obtain a test piece. A rosin-based flux was applied to the hardened material side of the composition of this test piece, and the solder layer flowing at 260 ° C for 60 seconds was washed with propylene glycol monomethyl ether acetate, and then washed with ethanol. About the test piece, the swelling or peeling of a coating film, and the change of a surface state were observed visually. Those who saw swelling or peeling of the coating film, and abnormalities such as dissolution or softening of the surface were evaluated as ×, and those who did not see it were evaluated as ○. The evaluation results are shown in Tables 13 to 15.

(Light-curing thermosetting composition) On a FR-4 copper-laminated laminated board having a size of 150 mm × 95 mm and a thickness of 1.6 mm, each composition shown in Tables 16 to 21 was formed with 80 mesh Tedlon regular twill The screen printing screen forms a comprehensive three-dimensional pattern. It is dried in a hot air circulation drying oven at 80 ° C for 30 minutes, and is fully exposed at 700 mJ / cm ² by a metal halide lamp exposure machine for printed wiring boards, using 1wt at 30 ° C. % Na ₂ CO ₃ developing solution, developed with a developing machine for 60 seconds. Then, the test piece was obtained by heat-hardening at 150 degreeC for 60 minutes in the hot-air circulation type drying furnace. A rosin-based flux was applied to the hardened material side of the composition of this test piece, and the solder layer flowing at 260 ° C for 60 seconds was washed with propylene glycol monomethyl ether acetate, and then washed with ethanol. The test piece was observed visually for swelling or peeling of the coating film, and for changes in the surface state. Those who saw swelling or peeling of the coating film, and abnormalities such as dissolution or softening of the surface were evaluated as ×, and those who did not see it were evaluated as ○. The evaluation results are shown in Tables 16 to 21.

[Insulation] (Thermosetting composition) Apply on a PET film with a thickness of 38 μm, apply each composition shown in Tables 13 to 15 with an applicator with a pitch of 120 μm, and dry it in a hot air circulation drying oven at 90 ° C. for 10 In minutes, a dry film of a resin layer having each composition was obtained. Thereafter, a test piece of IPC MULTI-PURPOSE TEST BOARD B-25 of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm-thick FR-4 substrate with a copper thickness of 35 μm was pressed on a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds. Second, the resin layer of each composition was bonded, the PET film was peeled off, and it was heated at 180 ° C. for 30 minutes in a hot-air circulation drying furnace to harden it. Next, cut off the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 as an electrically independent terminal (cut by the dotted line in Figure 3-2). Then, a bias of 500 VDC was applied to the upper part of the A test piece as the cathode and the lower part as the anode to measure the insulation resistance value. The evaluation was made as ○ when the insulation resistance value was 100 GΩ or more, and as X when the insulation resistance value was less than 100 GΩ. The results are shown in Tables 13 to 15.

(Photocurable thermosetting composition) Each of the compositions shown in Tables 16 to 21 was coated on a PET film having a thickness of 38 μm with an applicator having a pitch of 120 μm, and dried in a hot air circulation drying oven at 90 ° C. for 10 minutes. To obtain a dry film of a resin layer having each composition. Thereafter, a test piece of IPC MULTI-PURPOSE TEST BOARD B-25 of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm-thick FR-4 substrate with a copper thickness of 35 μm was pressed on a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds. In seconds, the resin layers of each composition were bonded, and the metal film was exposed at 700 mJ / cm ² by a metal halide lamp exposure machine for a printed wiring board. After that, the PET film was peeled off, and 1% by weight of Na ₂ CO ₃ at 30 ° C was used. The developing solution is developed by a developing machine for 60 seconds. Then, it heated at 150 degreeC for 60 minutes in the hot-air circulation type drying furnace, and hardened. Next, cut off the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 as an electrically independent terminal. Then, a bias of 500 VDC was applied to the upper part of the A test piece as the cathode and the lower part as the anode to measure the insulation resistance value. The evaluation was made as ○ when the insulation resistance value was 100 GΩ or more, and as X when the insulation resistance value was less than 100 GΩ. The results are shown in Tables 16 to 21.

[Relative permittivity and loss factor] (Thermosetting composition) Apply on a PET film with a thickness of 38 μm, apply each composition shown in Tables 13 to 15 with an applicator with a pitch of 200 μm, and apply it to a hot air circulation drying oven at 90 ° C. This was dried for 20 minutes to obtain a dry film of a resin layer having each composition. After that, the glossy side of the electrolytic copper foil with a thickness of 18 μm is facing up, and the base material of the FR-4 copper-laminated laminated board with a thickness of 1.6 mm is fixed with tape. For 60 seconds, the resin layers of each composition were laminated, the PET film was peeled off, and it was heated at 180 ° C for 30 minutes in a hot-air circulation drying furnace to harden it. Then, the fixed tape was peeled off, the electrolytic copper foil was peeled off, and cut into a size of 1.7 mm × 100 mm as a sample for evaluation. The measurement was performed using a hollow resonator (5 GHz) made by Kanto Electronics Application Development Co., Ltd. and a network analyzer E-507 made by Keysight Technologies. The relative permittivity was evaluated as ○ when the average of three measurements was less than 2.8, △ when 2.8 or more and less than 3.0, and X when 3.0 or more. The evaluation of the loss factor is set to ○ if the average of the three measurements is less than 0.02, and set to × when it is 0.02 or more. The results are shown in Tables 13 to 15 respectively.

(Photocurable thermosetting composition) Each composition shown in Tables 16 to 21 was coated on a PET film having a thickness of 38 μm with an applicator having a pitch of 200 μm, and dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. To obtain a dry film of a resin layer having each composition. After that, the glossy side of the electrolytic copper foil with a thickness of 18 μm is facing up, and the base material of the FR-4 copper-laminated laminated board with a thickness of 1.6 mm is fixed with tape. After pressing for 60 seconds, the resin layers of each composition were laminated, and an opening mask of 1.7 mm × 100 mm was used to expose the PET film with a metal halide lamp exposure machine at 700 mJ / cm ² after printing. The PET film was peeled off. Using a developer solution of 1 wt% Na ₂ CO ₃ at 30 ° C., the image was developed on a developing machine for 60 seconds. Then, it heated at 150 degreeC for 60 minutes in the hot-air circulation type drying furnace, and hardened. In addition, the fixed tape was peeled off, and the electrolytic copper foil was peeled off as a sample for evaluation. The measurement was performed using a hollow resonator (5 GHz) made by Kanto Electronics Application Development Co., Ltd. and a network analyzer E-507 made by Keysight Technologies. The evaluation of the relative permittivity was set to ○ when the average of three measurements was less than 3.0, Δ was set to 3.0 or more and less than 3.2, and Δ was set to 3.2 or more. The evaluation of the loss factor is set to ○ if the average of the three measurements is less than 0.02, and set to × when it is 0.02 or more. The results are shown in Tables 16 to 21, respectively.

* 3-1) Thermosetting resin 3-1: Epiclon HP-7200 cyclohexanone varnish (cyclic ether compound having a dicyclopentadiene skeleton) with a solid content of 50% by mass * 3-2) thermosetting resin 3-2: Tactix756 50% by mass cyclohexanone varnish (cyclic ether compound having a dicyclopentadiene skeleton) 3 * 3-3) thermosetting resin 3-3: Epiclon N-740 DIC (stock) Cyclohexanone varnish with solid content of 50% by mass * 3-4) Thermosetting resin 3-4: Epiclon 830 DIC (Co., Ltd.) * 3-5) Thermosetting resin 3-5: JER827 Mitsubishi Chemical Co., Ltd. * 3-6) Thermosetting resin 3-6: Resitop GDP-6085 solid content 60% by mass cyclohexanone varnish (phenol resin with dicyclopentadiene skeleton) 3 * 3-7) thermosetting resin 3- 7: HF-1 60% by mass of cyclohexanone varnish * 3-8) hardening catalyst manufactured by Meiwa Kasei Co., Ltd. 3-1: 2E4MZ (2-ethyl-4-methylimidazole) Shikoku Chemical Industry ( * 3-9) Filler 3-1: Adma Fine SO-C2 (share) Admatechs (silica dioxide) 3 * 3-10) Organic solvent 3-1: dimethylformamide * 3-11) Defoaming agent 3-1: BYK-352 Big Chemie Japan

* 3-18) Filler 3-2: B-30 Barium sulfate made by Sakai Chemical Industry Co., Ltd. * 3-19) Filler 3-3: DAW-07 Denka (stock) Alumina * 3-20) Dispersant 3 -1: DISPERBYK-111 manufactured by Big Chemie

* 3-12) hardening catalyst 3-2: finely pulverized melamine made by Nissan Chemical Co., Ltd. * 3-13) hardening catalyst 3-3: dicyanodiamide * 3-14) photopolymerization initiator 3 -1: Irgacure 907 BASF Co., Ltd. * 3-15) photocurable resin 3-1: dipentaerythritol tetraacrylate * 3-16) thermosetting resin 3-8: TEPIC-H (triglycidyl isocyanate) ) Nissan Chemical Co., Ltd. * 3-17) Colorant 3-1: Titanium Blue

From the results described in Tables 13 to 21, it was clearly confirmed that fine particles such as fine cellulose fibers and cyclic ether compounds having a dicyclopentadiene skeleton and phenol having a dicyclopentadiene skeleton were selected. At least one of the resin groups can obtain a curable resin composition having excellent insulation reliability, low dielectric properties, and good adhesion between the cured material and the plated copper. In addition, from the results of the evaluation of the solder heat resistance, it was confirmed that the compositions of the examples are excellent in heat resistance or chemical resistance, and can be used as a composition for wiring boards.

<Fourth Example> As the fine cellulose fibers CNF1 to CNF3 and cellulose nanocrystal particles CNC1 and CNC2, the same manufacturing examples 1 to 5 as those in the first embodiment were used, and as the varnishes 1 to 3, the same as the first varnish 1 to 3 were used. The second embodiment is the same as the synthesis examples 1 to 3.

According to the descriptions in the following Tables 22 to 30, after mixing and stirring each component, the high-pressure homogenizer Nanovater NVL-ES008 manufactured by Yoshida Machinery Industrial Co., Ltd. was repeated 6 times to disperse and prepare each composition. The numerical values in Tables 22 to 30 represent parts by mass.

[Solder heat resistance] (Thermosetting composition) On a FR-4 copper-clad laminate with a size of 150 mm × 95 mm and a thickness of 1.6 mm, each composition shown in Tables 22 to 25 is obliquely tilted with 80 mesh Tedlon The cloth pattern screen printing is used to form a comprehensive three-dimensional pattern, and it is dried in a hot air circulation drying oven at 80 ° C for 30 minutes, and then heated and hardened at 180 ° C for 30 minutes to obtain a test piece. A rosin-based flux was applied to the hardened material side of the composition of this test piece, and the solder layer flowing at 260 ° C for 60 seconds was washed with propylene glycol monomethyl ether acetate, and then washed with ethanol. About the test piece, the swelling or peeling of a coating film, and the change of a surface state were observed visually. Those who saw swelling or peeling of the coating film, and abnormalities such as dissolution or softening of the surface were evaluated as ×, and those who did not see it were evaluated as ○. The evaluation results are shown in Tables 22 to 25.

(Light-curing thermosetting composition) On a FR-4 copper-laminated laminated board having a size of 150 mm × 95 mm and a thickness of 1.6 mm, each composition shown in Tables 26 to 30 was formed with a 80-mesh Tedlon regular twill The screen printing screen forms a comprehensive three-dimensional pattern. It is dried in a hot air circulation drying oven at 80 ° C for 30 minutes, and is fully exposed at 700 mJ / cm ² by a metal halide lamp exposure machine for printed wiring boards, using 1wt at 30 ° C. % Na ₂ CO ₃ developing solution, developed with a developing machine for 60 seconds. Then, the test piece was obtained by heat-hardening at 150 degreeC for 60 minutes in the hot-air circulation type drying furnace. A rosin-based flux was applied to the hardened material side of the composition of this test piece, and the solder layer flowing at 260 ° C for 60 seconds was washed with propylene glycol monomethyl ether acetate, and then washed with ethanol. The test piece was observed visually for swelling or peeling of the coating film, and for changes in the surface state. Those who saw swelling or peeling of the coating film, and abnormalities such as dissolution or softening of the surface were evaluated as ×, and those who did not see it were evaluated as ○. The evaluation results are shown in Tables 26 to 30.

[Insulation] (Thermosetting composition) Apply on a PET film with a thickness of 38 μm, apply each composition shown in Tables 22 to 25 with an applicator with a pitch of 120 μm, and dry it in a hot air circulation drying oven at 90 ° C. for 10 In minutes, a dry film of a resin layer having each composition was obtained. Thereafter, a test piece of IPC MULTI-PURPOSE TEST BOARD B-25 of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm-thick FR-4 substrate with a copper thickness of 35 μm was pressed on a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds. Second, the resin layer of each composition was bonded, the PET film was peeled off, and it was heated at 180 ° C. for 30 minutes in a hot-air circulation drying furnace to harden it. Next, cut off the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 as an electrically independent terminal (cut by the dotted line in Figure 4-2). Then, a bias of 500 VDC was applied to the upper part of the A test piece as the cathode and the lower part as the anode to measure the insulation resistance value. The evaluation was made as ○ when the insulation resistance value was 100 GΩ or more, and as X when the insulation resistance value was less than 100 GΩ. The results are shown in Tables 22 to 25.

(Photocurable thermosetting composition) Each composition shown in Tables 26 to 30 was coated on a PET film having a thickness of 38 μm with an applicator having a pitch of 120 μm, and dried in a hot air circulation drying oven at 90 ° C. for 10 minutes. To obtain a dry film of a resin layer having each composition. Thereafter, a test piece of IPC MULTI-PURPOSE TEST BOARD B-25 of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm-thick FR-4 substrate with a copper thickness of 35 μm was pressed on a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds. In seconds, the resin layers of each composition were bonded, and the metal film was exposed at 700 mJ / cm ² by a metal halide lamp exposure machine for a printed wiring board. After that, the PET film was peeled off, and 1% by weight of Na ₂ CO ₃ at 30 ° C was used. The developing solution is developed by a developing machine for 60 seconds. Then, it heated at 150 degreeC for 60 minutes in the hot-air circulation type drying furnace, and hardened. Next, cut off the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 as an electrically independent terminal. Then, a bias of 500 VDC was applied to the upper part of the A test piece as the cathode and the lower part as the anode to measure the insulation resistance value. The evaluation was made as ○ when the insulation resistance value was 100 GΩ or more, and as X when the insulation resistance value was less than 100 GΩ. The results are shown in Tables 26 to 30.

[Removability of stains] (Thermosetting resin composition) Apply on a PET film with a thickness of 38 μm, apply each composition shown in Tables 22 to 25 with an applicator with a pitch of 120 μm, and use a hot air circulation drying oven at 90 ° C. This was dried for 10 minutes to obtain a dry film of a resin layer having each composition. Thereafter, a FR-4 copper-clad laminated board (copper thickness: 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm was pressed by a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds, and each was bonded. The resin layer of the composition was stripped of the PET film, and heated at 180 ° C. for 30 minutes in a hot-air circulation drying oven to harden it to obtain a test piece. The test piece was punched with a carbon dioxide laser punch LC-2K212 (manufactured by Hitachi Via Mechanics) with a beam diameter of 100 μm. Next, a permanganic acid stain removal (manufactured by ATOTECH) was performed. The standard steps for decontamination are in the order of the expansion step (60 ° C for 5 minutes), the permanganate etching step (80 ° C for 20 minutes), and the neutralization step (40 ° C for 5 minutes), but the permanganate etching step is divided into 10 The test was performed in three stages of minutes, 15 minutes, and 20 minutes. In addition, the punched portion was observed with a scanning electron microscope JSM-6610LV (manufactured by JEOL Ltd.) at a magnification of 3500 times, and the presence or absence of stains on the copper surface was confirmed. The evaluation was made to be ○ for 10 minutes without permanganic acid etching, △ for 15 minutes without stain, and X for 20 minutes. The results are shown in Tables 22 to 25.

(Photocurable thermosetting resin composition) Each composition shown in Tables 26 to 30 was coated on a PET film having a thickness of 38 μm with an applicator having a pitch of 120 μm, and dried in a hot air circulation type drying oven at 90 ° C. for 10 minutes. In minutes, a dry film of a resin layer having each composition was obtained. Thereafter, a FR-4 copper-clad laminated board (copper thickness: 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm was pressed by a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds, and each was bonded. The resin layer of the composition was subjected to full exposure at 700 mJ / cm ² with a metal halide lamp exposure machine using a printed wiring board, and then the PET film was peeled off, and a 1% by weight Na ₂ CO ₃ developing solution at 30 ° C. was used. The developing machine develops 60 seconds. Then, it heated at 150 degreeC for 60 minutes in the hot-air circulation type drying furnace, and hardened. A test piece was obtained after hardening. The test piece was punched with a carbon dioxide gas laser punch LC-2K212 (manufactured by Hitachi Via Mechanics) with a beam diameter of 100 μm. Next, the test was performed in three steps of 10 minutes, 15 minutes, and 20 minutes in the permanganic acid etching step using a permanganic acid decontamination spot (manufactured by ATOTECH). In addition, the punched portion was observed with a scanning electron microscope JSM-6610LV (manufactured by Japan Electronics Co., Ltd.) at a magnification of 3500 times, and the presence or absence of stains on the copper surface was confirmed. The evaluation was made to be ○ for 10 minutes without permanganic acid etching, △ for 15 minutes without stain, and X for 20 minutes. The results are shown in Tables 26 to 30.

[Measurement of Peel Strength and Ra] (Thermosetting resin composition) Apply each composition shown in Tables 22 to 25 with an applicator with a pitch of 120 μm on a PET film with a thickness of 38 μm, and apply it to a hot air circulation drying oven at 90 It dried at 10 degreeC for 10 minutes, and obtained the dry film of the resin layer which has each composition. Thereafter, a FR-4 copper-clad laminated board (copper thickness: 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm was pressed by a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds, and each was bonded. The resin layer of the composition was peeled off from the PET film and heated at 180 ° C. for 30 minutes in a hot-air circulation drying oven to harden it. Next, using a permanganic acid decontamination spot (manufactured by ATOTECH), the time of the permanganic acid etching step was only 10 minutes in the example, and the comparative example was produced in two steps of 10 minutes and 20 minutes. As a surface roughness measurement of the sample, Ra (arithmetic average roughness) was measured using a photo-drying microscope Contour GT (manufactured by BRUKER). Ra means the arithmetic mean thickness. Draw a line at the center of the profile curve. Divide the total area on the curve obtained by the center line by the value of length. The larger the value, the larger the thickness, and the smaller the value, the higher the smoothness. In addition, Ra is based on JIS B0031: 2003. The results are shown in Tables 22 to 25.

Next, the test pieces from the end to the decontamination point were processed in the order of electroless copper plating (Thru-Cup PEA, manufactured by Uemura Industry Co., Ltd.) and electrolytic copper plating, and a copper plating treatment with a copper thickness of 25 μm was applied. Next, a tempering treatment was performed in a hot-air circulation-type drying furnace at 190 ° C for 60 minutes to obtain a test substrate to which a copper plating treatment was applied. The test substrate was cut to a width of 1 cm and a length of 7 cm or more. Using a small table tester EZ-SX manufactured by Shimadzu Corporation, a 90 ° printing peel mold was used to determine the peel strength at an angle of 90 degrees. In the evaluation, a value of 4.5 N / m or more was ○, a value of 2.5 N / m or more and less than 4.5 N / m was Δ, and a value of less than 2.5 N / m was x. The results are shown in Tables 22 to 25.

(Photocurable thermosetting resin composition) Each composition shown in Tables 26 to 30 was coated on a PET film having a thickness of 38 μm with an applicator having a pitch of 120 μm, and dried in a hot air circulation type drying oven at 90 ° C. for 10 minutes. In minutes, a dry film of a resin layer having each composition was obtained. Thereafter, a FR-4 copper-clad laminated board (copper thickness: 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm was pressed by a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds to bond each The resin layer of the composition was subjected to full exposure at 700 mJ / cm ² with a metal halide lamp exposure machine using a printed wiring board, and then the PET film was peeled off, and a 1% by weight Na ₂ CO ₃ developing solution at 30 ° C. was used. The developing machine develops 60 seconds. Then, it heated at 150 degreeC for 60 minutes in the hot-air circulation type drying furnace, and hardened. Next, using a permanganic acid decontamination spot (manufactured by ATOTECH), the time of the permanganic acid etching step was only 10 minutes in the example, and the comparative example was produced in two steps of 10 minutes and 20 minutes. As a surface roughness measurement of the sample, Ra was measured using a photo-drying microscope ContourGT (manufactured by BRUKER). The results are shown in Tables 26 to 30.

Next, the test pieces from the end to the decontamination point were processed in the order of electroless copper plating (Thru-Cup PEA, manufactured by Uemura Industry Co., Ltd.) and electrolytic copper plating, and a copper plating treatment with a copper thickness of 25 μm was applied. Next, a tempering treatment was performed in a hot-air circulation-type drying furnace at 190 ° C for 60 minutes to obtain a test substrate to which a copper plating treatment was applied. The test substrate was cut to a width of 1 cm and a length of 7 cm or more. Using a small table tester EZ-SX manufactured by Shimadzu Corporation, a 90 ° printing peel mold was used to determine the peel strength at an angle of 90 degrees. In the evaluation, a value of 4.5 N / m or more was ○, a value of 2.5 N / m or more and less than 4.5 N / m was Δ, and a value of less than 2.5 N / m was x. The results are shown in Tables 26 to 30.

* 4-1) Phenoxy resin 4-1: YX6954 Cyclohexanone varnish made of 30% by mass of Mitsubishi Chemical Co., Ltd. * 4-2) Phenoxy resin 4-2: 1256 solid form of Mitsubishi Chemical Co., Ltd. 30% by mass of cyclohexanone varnish * 4-3) Phenoxy resin 4-3: 4250 30% by mass of cyclohexanone varnish * 4-4) thermosetting resin 4-1 by Mitsubishi Chemical Corporation (solid) Cyclohexanone varnish 50% by mass of Epiclon N-740 DIC (stock) * 4-5) thermosetting resin 4-2: Epiclon 830 DIC (stock) * 4-6) thermosetting resin 4- 3: JER827 Mitsubishi Chemical Corporation (4-7) thermosetting resin 4-4: HF-1 Meiwa Kasei Corporation (solid) 60% by mass cyclohexanone varnish * 4-8) hardening catalyst 4- 1: 2E4MZ (2-ethyl-4-methylimidazole) Shikoku Chemical Industry Co., Ltd. * 4-9) Filler 4-1: Adma Fine SO-C2 (share) Admatechs (silica dioxide) * 4 -10) Organic solvent 4-1: dimethylformamide * 4-11) Antifoaming agent 4-1: BYK-352 Big Chemie Japan Co., Ltd.

* 4-18) Filler 4-2: B-30 Barium sulfate manufactured by Sakai Chemical Industry Co., Ltd. * 4-19) Filler 4-3: DAW-07 Denka (stock) Alumina * 4-20) Dispersant 4 -1: DISPERBYK-111 manufactured by Big Chemie

* 4-12) Hardening catalyst 4-2: Finely pulverized melamine made by Nissan Chemical Co., Ltd. * 4-13) Hardening catalyst 4-3: Dicyanodiamine * 4-14) Photopolymerization initiator 4 -1: Irgacure 907 BASF Co., Ltd. * 4-15) Photocurable resin 4-1: Dipentaerythritol tetraacrylate * 4-16) Thermosetting resin 4-5: TEPIC-H (Triglycidyl isocyanate) ) Nissan Chemical Co., Ltd. * 4-17) Colorant 4-1: Titanium Blue

From the results described in Tables 22 to 30, it can be clearly confirmed that by including fine powder such as fine cellulose fibers and phenoxy resin, stains caused by laser processing can be removed in a stain removing step, and at the same time, it has a favorable high Curable resin composition with small surface roughness and excellent peel strength with frequency transmission. In addition, from the results of the evaluation of the solder heat resistance, it was confirmed that the compositions of the examples are excellent in heat resistance or chemical resistance, and can be used as a composition for wiring boards.

<Fifth Example> As the fine cellulose fibers CNF1 to CNF3 and the cellulose nanocrystalline particles CNC1 and CNC2, the same manufacturing examples 1 to 5 as those in the first embodiment were used, and as the varnishes 1 to 3, the same as the first varnish 3 was used. The second embodiment is the same as the synthesis examples 1 to 3.

According to the descriptions in the following Tables 31 to 39, after mixing and stirring each component, a high-pressure homogenizer Nanovater NVL-ES008 manufactured by Yoshida Machinery Industries was used to disperse it 6 times to prepare each composition. The numerical values in Tables 31 to 39 represent parts by mass.

[Expansion of plated copper] (Thermosetting composition) Apply on a PET film with a thickness of 38 μm, apply each composition shown in Tables 31 to 33 with an applicator with a pitch of 120 μm, and use a hot-air circulation type drying oven at 90 ° C. This was dried for 10 minutes to obtain a dry film of a resin layer having each composition. Thereafter, a FR-4 copper-clad laminated board (copper thickness: 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm was pressed by a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds, and each was bonded. The resin layer of the composition was peeled off from the PET film and heated at 180 ° C. for 30 minutes in a hot-air circulation drying oven to harden it. Next, the treatment was performed in the order of permanganic acid decontamination (manufactured by ATOTECH), electroless copper plating (Thru-Cup PEA, manufactured by Uemura Industry Co., Ltd.), and electrolytic copper plating treatment, and copper plating with a copper thickness of 25 μm was applied. Applied treatment. Next, a tempering treatment was performed in a hot-air circulation-type drying furnace at 190 ° C for 60 minutes to obtain a test substrate to which a copper plating treatment was applied. In addition, after passing through the reflow furnace at a peak temperature of 265 ° C three times, the swelling of the plated copper was visually evaluated. Among the 10 test substrates, there was no swelling at all, ○, among the 10 test substrates, there was swelling within Δ, and at least 2 of the 10 test substrates had swelling, x. The results are shown in Tables 31 to 33.

(Photocurable thermosetting composition) Each of the compositions shown in Tables 34 to 39 was coated on a PET film having a thickness of 38 μm with an applicator having a pitch of 120 μm, and dried in a hot air circulation drying oven at 90 ° C. for 10 minutes. To obtain a dry film of a resin layer having each composition. Thereafter, a FR-4 copper-clad laminated board (copper thickness: 18 μm) having a size of 150 mm × 100 mm and a thickness of 1.6 mm was pressed by a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds, and each was bonded. The resin layer of the composition was subjected to full exposure at 700 mJ / cm ² with a metal halide lamp exposure machine using a printed wiring board, and then the PET film was peeled off, and a 1% by weight Na ₂ CO ₃ developing solution at 30 ° C. was used. The developing machine develops 60 seconds. Then, it heated at 150 degreeC for 60 minutes in the hot-air circulation type drying furnace, and hardened. Next, the treatment was performed in the order of permanganic acid decontamination (manufactured by ATOTECH), electroless copper plating (Thru-Cup PEA, manufactured by Uemura Industry Co., Ltd.), and electrolytic copper plating treatment, and copper plating with a copper thickness of 25 μm was applied. Applied treatment. Next, a tempering treatment was performed in a hot-air circulation-type drying furnace at 190 ° C for 60 minutes to obtain a test substrate to which a copper plating treatment was applied. In addition, after passing through the reflow furnace at a peak temperature of 265 ° C three times, the swelling of the plated copper was visually evaluated. Among the 10 test substrates, there was no swelling at all, ○, among the 10 test substrates, there was swelling within Δ, and at least 2 of the 10 test substrates had swelling, x. The results are shown in Tables 34 to 39.

[Solder heat resistance] (Thermosetting composition) On a FR-4 copper-laminated laminated board with a size of 150 mm × 95 mm and a thickness of 1.6 mm, each composition shown in Tables 31 to 33 is obliquely inclined at 80 mesh The cloth pattern screen printing is used to form a comprehensive three-dimensional pattern, and it is dried in a hot air circulation drying oven at 80 ° C for 30 minutes, and then heated and hardened at 180 ° C for 30 minutes to obtain a test piece. A rosin-based flux was applied to the hardened material side of the composition of this test piece, and the solder layer flowing at 260 ° C for 60 seconds was washed with propylene glycol monomethyl ether acetate, and then washed with ethanol. About the test piece, the swelling or peeling of a coating film, and the change of a surface state were observed visually. Those who saw swelling or peeling of the coating film, and abnormalities such as dissolution or softening of the surface were evaluated as ×, and those who did not see it were evaluated as ○. The evaluation results are shown in Tables 31 to 33.

(Photo-curable thermosetting composition) On a FR-4 copper-laminated laminated board having a size of 150 mm × 95 mm and a thickness of 1.6 mm, each of the compositions shown in Tables 34 to 39 was patterned with a 80-mesh Tedlon dragon twill. The screen printing screen forms a comprehensive three-dimensional pattern. It is dried in a hot air circulation drying oven at 80 ° C for 30 minutes, and is fully exposed at 700 mJ / cm ² by a metal halide lamp exposure machine for printed wiring boards, using 1wt at 30 ° C. % Na ₂ CO ₃ developing solution, developed with a developing machine for 60 seconds. Then, the test piece was obtained by heat-hardening at 150 degreeC for 60 minutes in the hot-air circulation type drying furnace. A rosin-based flux was applied to the hardened material side of the composition of this test piece, and the solder layer flowing at 260 ° C for 60 seconds was washed with propylene glycol monomethyl ether acetate, and then washed with ethanol. The test piece was observed visually for swelling or peeling of the coating film, and for changes in the surface state. Those who saw swelling or peeling of the coating film, and abnormalities such as dissolution or softening of the surface were evaluated as ×, and those who did not see it were evaluated as ○. The evaluation results are shown in Tables 34 to 39.

[Insulation] (Thermosetting composition) Apply on a PET film with a thickness of 38 μm, apply each composition shown in Tables 31 to 33 with an applicator with a pitch of 120 μm, and dry it at 90 ° C in a hot-air circulation drying oven. 10 In minutes, a dry film of a resin layer having each composition was obtained. Thereafter, a test piece of IPC MULTI-PURPOSE TEST BOARD B-25 of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm-thick FR-4 substrate with a copper thickness of 35 μm was pressed on a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds. Second, the resin layer of each composition was bonded, the PET film was peeled off, and it was heated at 180 ° C. for 30 minutes in a hot-air circulation drying furnace to harden it. Next, cut off the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 as an electrically independent terminal (cut by the dotted line in Figure 5-2). Then, a bias of 500 VDC was applied to the upper part of the A test piece as the cathode and the lower part as the anode to measure the insulation resistance value. The evaluation was made as ○ when the insulation resistance value was 100 GΩ or more, and as X when the insulation resistance value was less than 100 GΩ. The results are shown in Tables 31 to 33.

(Photocurable thermosetting composition) Each of the compositions shown in Tables 34 to 39 was coated on a PET film having a thickness of 38 μm with an applicator having a pitch of 120 μm, and dried in a hot air circulation drying oven at 90 ° C. for 10 minutes. To obtain a dry film of a resin layer having each composition. Thereafter, a test piece of IPC MULTI-PURPOSE TEST BOARD B-25 of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm-thick FR-4 substrate with a copper thickness of 35 μm was pressed on a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds. In seconds, the resin layers of each composition were bonded, and the metal film was exposed at 700 mJ / cm ² by a metal halide lamp exposure machine for a printed wiring board. After that, the PET film was peeled off, and 1% by weight of Na ₂ CO ₃ at 30 ° C was used. The developing solution is developed by a developing machine for 60 seconds. Then, it heated at 150 degreeC for 60 minutes in the hot-air circulation type drying furnace, and hardened. Next, cut off the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 as an electrically independent terminal. Then, a bias of 500 VDC was applied to the upper part of the A test piece as the cathode and the lower part as the anode to measure the insulation resistance value. The evaluation was made as ○ when the insulation resistance value was 100 GΩ or more, and as X when the insulation resistance value was less than 100 GΩ. The results are shown in Tables 34 to 39.

[Production of a sample for measuring thermal expansion] (Thermosetting resin composition) Apply each composition shown in Tables 31 to 33 on a PET film with a thickness of 38 μm, with an applicator with a pitch of 120 μm, and apply it to a hot air circulation drying oven at 90 ° C. It dried at 10 degreeC for 10 minutes, and obtained the dry film of the resin layer which has each composition. Thereafter, a copper foil having a thickness of 18 μm was pressed with a vacuum laminator at 60 ° C. and a pressure of 0.5 MPa for 60 seconds, and the resin layers of the respective compositions were laminated to peel off the PET film. Next, it was heated at 180 ° C. for 30 minutes in a hot-air circulation drying furnace to harden it, and the copper foil was peeled to obtain a sample of a cured film.

(Photocurable thermosetting resin composition) A copper foil with a thickness of 18 μm was attached to a FR-4 copper-clad laminate with a thickness of 1.6 mm, and each composition shown in Tables 34 to 39 was applied with an applicator with a pitch of 120 μm. , And dried in a hot air circulation type drying oven at 90 ° C for 10 minutes. After that, it was brought into close contact with a negative mask having a pattern of 3 mm width × 30 mm length, and exposed at 700 mJ / cm ² with a metal halide lamp exposure machine for a printed wiring board. Next, a developing solution of 1 wt% Na ₂ CO ₃ at 30 ° C. was used to develop for 60 seconds on a developing machine. Then, it heated at 150 degreeC in the hot-air circulation type drying furnace, and hardened for 60 minutes, and peeled the copper foil, and obtained the sample of a hardened film.

[Measurement of Thermal Expansion Ratio] (Thermosetting resin composition) 制作 The produced sample for thermal expansion measurement was cut into a width of 3 mm × length of 30 mm. TMA (Thermome Mechanical Analysis) Q400 manufactured by TA Instrument was used for this test piece, and the chuck pitch was 16 mm in a tensile mode, and a load of 30 mN was heated to 20 to 250 ° C. at 5 ° C./min in a nitrogen environment, and then 5 ° C./min. Measure the temperature by reducing the temperature to 250 ~ 20 ℃ in minutes. Calculate the average thermal expansion coefficient α1 from 30 ° C to 100 ° C and the average thermal expansion coefficient α2 from 200 ° C to 230 ° C when the temperature is lowered. The evaluation is performed based on the value. When α1 is less than 25 ppm, it is ○, if it is less than 35 ppm, it is Δ, and if it is 35 ppm or more, it is ×. When α2 is less than 75 ppm, it is ○; when it is less than 95 ppm, it is △; The results are shown in Tables 31 to 33.

(Photocurable thermosetting resin composition) 进行 Except that the produced sample was used as it is, it was performed in the same manner as the thermosetting resin composition. The results are shown in Tables 34 to 39.

* 5-1) Thermosetting resin 5-1: NC-3000H Cyclohexanone varnish (cyclic ether compound with biphenyl skeleton) with a solid content of 50% by mass produced by Nippon Kayaku Co., Ltd. * 5-2) Heat Curable resin 5-2: YX-4000 Mitsubishi Chemical Co., Ltd. 50% by mass solid cyclohexanone varnish (cyclic ether compound with biphenyl skeleton) 5 * 5-3) thermosetting resin 5-3: Epiclon N-740 DIC (stock) solid cyclopentanone varnish 50% by mass * 5-4) thermosetting resin 5-4: Epiclon 830 DIC (stock) * 5-5) thermosetting resin 5- 5: JER827 Mitsubishi Chemical Corporation * 5-6) thermosetting resin 5-6: GPH-103 Nippon Kayaku Co., Ltd. solid content 60% by mass cyclohexanone varnish (phenol resin with biphenyl skeleton) * 5-7) Thermosetting resin 5-7: HF-1 60% by mass of cyclohexanone varnish made by Meiwa Kasei Co., Ltd. * 5-8) Hardening catalyst 5-1: 2E4MZ (2-ethyl- 4-methylimidazole) Shikoku Chemical Industry Co., Ltd. * 5-9) Filler 5-1: Adma Fine SO-C2 (shares) Admatechs (Silicon Dioxide) * 5-10) Organic solvent 5-1: Dimethylformamide * 5-11) Antifoaming agent 5-1: BYK-352 Big Chemie Japan Co., Ltd.

* 5-18) Thermosetting resin 5-8: Bisphenol A diacetate manufactured by Tokyo Chemical Industry Co., Ltd. (active ester compound)

* 5-19) Filler 5-2: B-30 Barium sulfate manufactured by Sakai Chemical Industry Co., Ltd. * 5-20) Filler 5-3: DAW-07 Denka (share) Alumina * 5-21) Dispersant 5 -1: DISPERBYK-111 manufactured by Big Chemie

* 5-12) Hardening catalyst 5-2: Finely pulverized melamine Nissan Chemical Co., Ltd. * 5-13) Hardening catalyst 5-3: Dicyanodiamine * 5-14) Photopolymerization initiator 5 -1: Irgacure 907 BASF Co., Ltd. * 5-15) Photocurable resin 5-1: Dipentaerythritol tetraacrylate * 5-16) Thermosetting resin 5-9: TEPIC-H (Triglycidyl isocyanate) ) Nissan Chemical Co., Ltd. * 5-17) Colorant 5-1: Titanium Blue

From the results described in Tables 31 to 39, it was clearly confirmed that at least 1 was selected from the group consisting of fine powder such as fine cellulose fibers and a cyclic ether compound having a biphenyl skeleton and a phenol resin having a biphenyl skeleton. It is possible to obtain a curable resin composition which can obtain low thermal expansion properties, and even when the plated copper is formed in a solid state on the hardened material of the composition, the plated copper does not expand due to thermal history. Of hardened. In addition, from the results of the evaluation of the solder heat resistance, it was confirmed that the compositions of the examples are excellent in heat resistance or chemical resistance, and can be used as a composition for wiring boards.

<Sixth Example> As cellulose nanocrystal particles CNC1 and CNC2, the same manufacturing examples 4 and 5 as in the first embodiment were used.

According to the descriptions in the following Tables 40 and 41, after mixing and stirring each component, a high-pressure homogenizer Nanovater NVL-ES008 manufactured by Yoshida Machinery Industries was used to disperse it 6 times to prepare each composition. The values in Tables 40 and 41 represent parts by mass. About each composition obtained by the Example and the comparative example, the thermal expansion coefficient, heat resistance, insulation, toughness (tensile rate), and the lifetime were evaluated. The evaluation method is as follows.

[Coefficient of Thermal Expansion] 涂布 Apply each composition on a PET film with a thickness of 38 μm using an applicator with a pitch of 120 μm, and dry it at 90 ° C. for 10 minutes in a hot-air circulation drying furnace to obtain a dry film with a resin layer of each composition. Thereafter, a copper foil having a thickness of 18 μm was pressed with a vacuum laminator at 60 ° C. and a pressure of 0.5 MPa for 60 seconds, and the resin layers of the respective compositions were laminated to peel off the PET film. Next, it was heated at 180 ° C. for 30 minutes in a hot-air circulation drying furnace to harden it, and was peeled from the copper foil to obtain a thin film sample made of the hardened material of each composition. The obtained film sample was cut into a length of 3 mm × 30 mm as a test piece for measuring the thermal expansion coefficient. About this test piece, TMA (Thermome Mechanical Analysis) Q400 manufactured by TA Instrument was used, the chuck pitch was 16 mm in a tensile mode, and a load of 30 mN was heated to 20 to 250 ° C. at 5 ° C./min in a nitrogen environment, and then at 5 ° C. The temperature is reduced to 250 ~ 20 ° C / min, and the thermal expansion coefficients α1 and α2 (ppm / K) are measured. These measurement results are combined and shown in Tables 40 and 41.

[Heat resistance] Apply each composition on a PET film having a thickness of 38 μm using an applicator with a pitch of 120 μm, and dry it at 90 ° C. for 10 minutes in a hot air circulation drying oven to obtain a dry film having a resin layer of each composition. Thereafter, a copper foil having a thickness of 18 μm was pressed with a vacuum laminator at 60 ° C. and a pressure of 0.5 MPa for 60 seconds, and the resin layers of the respective compositions were laminated to peel off the PET film. Next, it was heated at 180 ° C. for 30 minutes in a hot-air circulation drying furnace to harden it, and was peeled from the copper foil to obtain a thin film sample made of the hardened material of each composition. The obtained film sample was pulverized in a mortar made of agate, and a 3% by weight heating weight reduction temperature was confirmed and evaluated by a TG curve measured at a temperature increase rate of 10 ° C / min under a nitrogen stream in accordance with JIS-K-7120. The evaluation criterion is 3% by weight if the heating weight reduction temperature is less than 300 ° C, and X, 300 ° C or more and 310 ° C or less, and Δ, and 310 ° C or more.

[Insulation] Apply each composition on a PET film with a thickness of 38 μm using an applicator with a pitch of 120 μm, and dry it at 90 ° C. for 10 minutes in a hot air circulation drying oven to obtain a dry film with a resin layer of each composition. Thereafter, a test piece of IPC MULTI-PURPOSE TEST BOARD B-25 of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm-thick FR-4 substrate with a copper thickness of 35 μm was pressed on a vacuum bonding machine at 60 ° C. and a pressure of 0.5 MPa for 60 seconds. Second, the resin layer of each composition was bonded, the PET film was peeled off, and it was heated at 180 ° C. for 30 minutes in a hot-air circulation drying furnace to harden it. Next, cut off the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 as an electrically independent terminal (cut by the dotted line in Figure 6-4). In addition, the test piece A was made into the cathode and the lower part was the anode, and a bias voltage of 500 VDC was applied, and the insulation resistance value was measured and evaluated. The evaluation criterion is set to ○ if the insulation resistance value is 100 GΩ or more, and × when the insulation resistance value is less than 100 GΩ. The evaluation results are shown in Tables 40 and 41.

[Toughness] Apply each composition on a PET film with a thickness of 38 μm with an applicator with a pitch of 200 μm, and dry it in a hot air circulation drying oven at 90 ° C. for 20 minutes to obtain a dry film with a resin layer of each composition. Next, an electrolytic copper foil with a thickness of 18 μm and a glossy side facing upward was fixed on a FR-4 copper-laminated laminate with a thickness of 1.6 mm with a tape, and the dry film was vacuum-bonded with a 60 ° C. pressure 0.5 MPa. The resin layer of each composition was laminated on the electrolytic copper foil under pressure for 60 seconds under conditions, and then the PET film was peeled off and heated at 180 ° C. for 30 minutes in a hot-air circulation drying furnace to harden the resin layer. Then, the fixed tape was peeled, and the electrolytic copper foil was further peeled to obtain a thin film sample made of a resin layer. Next, the above-mentioned film sample was cut to a specific size in accordance with JIS K7127 to prepare a test piece for evaluation. For this test piece, a small table tester EZ-SX manufactured by Shimadzu Corporation was used to measure the stress [MPa] and skew [%] at a pulling speed of 10 mm / min. The skewness [%] at this time is the elongation at the time of breaking the test piece. The larger the toughness, the higher the toughness evaluation. Therefore, the skewness [%] is used to evaluate the toughness. The evaluation criterion is that the skewness [%] is less than 2.0% and is set to ×, and the 2.0% or more is set to 0. The evaluation results are shown in Tables 40 and 41.

[Term of use] The viscosity of each composition after dispersion is measured using a cone and plate viscometer TPE-100-H manufactured by Toki Sangyo, and the initial viscosity is set. After that, it was placed in an airtight container at a temperature of 23 ° C., and the viscosity was measured and evaluated after 48 hours and 96 hours. The evaluation criterion is 0 if the rate of increase in viscosity after 30 hours is 30%, the rate of increase after 30 hours is within 30% is Δ, and the rate of increase after 48 hours is 30% or higher. × can be used for a short time, so when a liquid or film is stored from low temperature to normal temperature, if the next step is not carried out early, problems may occur, but ○ can be used for a long time, so Even if it is a liquid or film, it is easier to handle.

* 6-1) Thermosetting resin 6-1: Cyclohexanone varnish (cyclic ether compound with naphthalene skeleton) made of 50% by mass of Epiclon HP-4032 DIC (strand) * 6-2) thermosetting Resin 6-2: NC-7300L Cyclohexanone varnish (cyclic ether compound with naphthalene skeleton) made of 50% by mass of Nippon Kayaku Co., Ltd. 6 * 6-3) Thermosetting resin 6-3: YX- 8800 Cyclohexanone varnish (cyclic ether compound with onion skeleton) made by Mitsubishi Chemical Corporation (50% by mass) 固 * 6-4) thermosetting resin 6-4: Epiclon HP-7200 by 50% by mass Cyclohexanone varnish (cyclic ether compound with a dicyclopentadiene skeleton) 6 * 6-5) Thermosetting resin 6-5: NC-3000H Cyclohexanone with a solid content of 50% by mass of Nippon Kayaku Co., Ltd. Varnish (Cyclic ether compound with biphenyl skeleton) 6 * 6-6) Thermosetting resin 6-6: YX-4000 Mitsubishi Chemical Co., Ltd. 50% by mass solid cyclohexanone varnish (with biphenyl skeleton) Cyclic ether compound) * 6-7) Thermosetting resin 6-7: Epiclon N-740 DIC (strand) 50% by mass of cyclohexanone varnish * 6-8) thermosetting resin 6-8: Epiclon 830 DIC (shares) system * 6-9) Thermosetting resin 6-9: JER827 made by Mitsubishi Chemical Corporation * 6-10) Phenoxy resin 6-1: YX6954 30% by mass of cyclohexanone varnish made by Mitsubishi Chemical Corporation * 6 -11) Hardener 6-1: HF-1 60% by mass of cyclohexanone varnish made by Meiwa Kasei Co., Ltd. * 6-12) Hardener 6-2: Bisphenol A diacetate Tokyo Chemical Industry Co., Ltd. ) (Active ester) * 6-13) hardening catalyst 6-1: 2E4MZ (2-ethyl-4-methylimidazole) Shikoku Chemical Industry Co., Ltd. * 6-14) filler 6-1: Adma Fine SO-C2 (share) Admatechs (silica dioxide) 6 * 6-15) Organic solvent 6-1: dimethylformamide * 6-16) Defoamer 6-1: BYK-352 Big Chemie Japan ( * 6-17) cellulose powder: NP fiber W-06MG (average particle diameter 6 μm) made in Japan

From the results described in Tables 40 and 41, it is clearly confirmed that by using fillers other than cellulose nanocrystal particles and cellulose nanocrystal particles in combination, it is possible to obtain not only normal temperature in a high-temperature region during component mounting, but also low thermal expansion can be maintained. The cured product is excellent in various properties such as toughness, heat resistance, and the like, and a curable resin composition having excellent life span is obtained. In addition, although Tables 40 and 41 are not described, it was confirmed that the relative permittivity and the loss factor can be reduced by using the active ester as a curing agent.

<Seventh Example> [Preparation of fine cellulose fibers] Manufacturing Example 6 (CNF dispersion 1) 针 After coniferous tree bleached kraft pulp fibers (Machenzie CSF650ml, manufactured by Fletcher Challenge Canada) were sufficiently stirred with 9900 g of ion-exchanged water, TEMPO (2,2,6,6-tetramethylpiperidine 1-oxy radical produced by ALDRICH), 12.5% by mass of sodium bromide, 28.4% by weight were sequentially added to 100 g of the sludge mass. Mass% sodium hypochlorite. Using pH-stat, 0.5 M sodium hydroxide was dropped and the pH was maintained at 10.5. After the reaction was performed for 120 minutes (20 ° C), the dropping of sodium hydroxide was stopped to obtain an oxidized slurry.充分 Wash the obtained oxidized slurry with ion-exchanged water, and then perform dehydration treatment. Thereafter, 3.9 g of the oxidized slurry and 296.1 g of ion-exchanged water were subjected to a refining treatment twice at 245 MPa using a high-pressure homogenizer (manufactured by Sugino machine, Starburst Lab HJP 2 5005) to obtain a fine cellulose fiber dispersion liquid containing carboxyl groups. (Solid content concentration: 1.3% by mass).

Next, 4087.75 g of the obtained carboxyl-containing fine cellulose fiber dispersion was placed in a beaker, and 4085 g of ion-exchanged water was added as a 0.5% by mass aqueous solution, followed by stirring at room temperature (25 ° C) for 30 minutes with a mechanical stirrer. Next, 245 g of a 1 M aqueous hydrochloric acid solution was added, and reacted at room temperature for 1 hour. After completion of the reaction, it was reprecipitated with acetone. After filtration, it was washed with acetone / ion-exchanged water to remove hydrochloric acid and salts. Finally, acetone was added and filtered to obtain an acetone-containing acid-based cellulose fiber dispersion (solid content concentration: 5.0% by mass) in which carboxyl-containing fine cellulose fibers were swollen in acetone. After completion of the reaction, the mixture was filtered, and then washed with ion-exchanged water to remove hydrochloric acid and salts. Furthermore, the solvent was substituted with acetone to obtain a dispersion liquid having a solid content adjusted to 5.0% by mass. Next, 250 g of Epiclon 830 DIC (bisphenol F-type epoxy resin) and JER827 Mitsubishi Chemical Corporation (bisphenol A-type epoxy resin) 100g and ELM100 Sumitomo Chemical Industries (stock) An epoxy resin with amines as precursors: 250 g of triglycidylaminophenol) and 1000 g of a dispersion liquid in which the aforementioned acetone was used as a solvent and the solid content was adjusted to 5.0% by mass. After stirring, the acetone was removed by an evaporator to obtain Acid type cellulose fiber dispersion of epoxy resin (average fiber diameter: 3.3 nm, CNF concentration: 7.7% by mass).

Manufacturing Example 7 (CNF dispersion 2) 针 Bleached kraft pulp mud fibers (Machenzie CSF650ml, manufactured by Fletcher Challenge Canada, Inc.) with 9900 g of ion-exchanged water were sufficiently stirred, and then 1.25% by mass was added to 100 g of the pulp mass in this order. TEMPO (2,2,6,6-tetramethylpiperidine 1-oxy radical produced by ALDRICH), 12.5 mass% sodium bromide, and 28.4 mass% sodium hypochlorite. Using pH-stat, 0.5 M sodium hydroxide was dropped and the pH was maintained at 10.5. After the reaction was performed for 120 minutes (20 ° C), the dropping of sodium hydroxide was stopped to obtain an oxidized slurry.充分 Wash the obtained oxidized slurry with ion-exchanged water, and then perform dehydration treatment. Thereafter, 3.9 g of the oxidized slurry and 296.1 g of ion-exchanged water were subjected to a refining treatment twice at 245 MPa using a high-pressure homogenizer (manufactured by Sugino machine, Starburst Lab HJP 2 5005) to obtain a fine cellulose fiber dispersion liquid containing carboxyl groups. (Solid content concentration: 1.3% by mass).

Next, 4087.75 g of the obtained carboxyl-containing fine cellulose fiber dispersion was placed in a beaker, and 4085 g of ion-exchanged water was added as a 0.5% by mass aqueous solution, followed by stirring at room temperature (25 ° C) for 30 minutes with a mechanical stirrer. Next, 245 g of a 1 M aqueous hydrochloric acid solution was added, and reacted at room temperature for 1 hour. After completion of the reaction, it was reprecipitated with acetone. After filtration, it was washed with acetone / ion-exchanged water to remove hydrochloric acid and salts. Finally, acetone was added and filtered to obtain an acetone-containing acid-based cellulose fiber dispersion (solid content concentration: 5.0% by mass) in which carboxyl-containing fine cellulose fibers were swollen in acetone. After completion of the reaction, after filtration, the solution was washed with ion-exchanged water to remove hydrochloric acid and salts. After solvent substitution with acetone, solvent substitution with DMF, an acidic cellulose fiber dispersion containing DMF in an expanded state with fine cellulose fibers containing carboxyl groups (average fiber diameter of 3.3 nm, solid content concentration of 5.0% by mass) was obtained. .

400 g of the obtained DMF-containing acidic cellulose fiber dispersion liquid and 3 g of hexylamine were placed in a beaker equipped with an electromagnetic stirrer and a stirrer, and dissolved in 3000 g of ethanol. The reaction solution was allowed to react at room temperature (25 ° C) for 6 hours. After the reaction was completed, filtration was performed, and washing with DMF and solvent substitution were performed to obtain a fine cellulose fiber composite (solid content concentration of 5.0% by mass) in which fine cellulose fibers were linked to an amine via an ion bond. Next, 25 g of Epiclon 830 DIC (bisphenol F-type epoxy resin) and JER827 Mitsubishi Chemical Corporation (bisphenol A-type epoxy resin) 10 g were mixed with ELM100 Sumitomo Chemical Industries (stock) Epoxy resin with amines as precursors: Triglycidylaminophenol) 25g and the aforementioned fine cellulose fibers, 200g of fine cellulose fiber composites with amines connected via an ionic bond, DMF is removed by an evaporator after stirring, A fine cellulose fiber composite (CNF concentration: 15.4% by mass) was obtained in which fine cellulose fibers containing epoxy resin were bonded to an amine via an ion bond. The CNF produced by the method of Production Example 7 is particularly good in dispersibility, and can be dispersed by a general method without using a special disperser such as a high-pressure homogenizer.

Production Example 8 (CNF Dispersion 3) 脱水 10% by mass of fine cellulose fibers (BiNFi-s manufactured by Sugino Machine Co., Ltd., average fiber diameter 80nm) was dehydrated and filtered, and 10 times the amount of acetone as the mass of the filter substance was added and stirred for 30 minutes. filter. The replacement operation was repeated three times, and 20 times the amount of acetone as the mass of the filter was added to prepare a fine cellulose fiber dispersion (solid content concentration: 5.0% by mass). Next, 250 g of Epiclon 830 DIC (bisphenol F-type epoxy resin) and JER827 Mitsubishi Chemical Corporation (bisphenol A-type epoxy resin) 100g and ELM100 Sumitomo Chemical Industries (stock) An epoxy resin containing amines as a precursor: triglycidylaminophenol) was mixed with 1,000 g of the aforementioned fine cellulose fiber dispersion, and the acetone was removed by an evaporator after stirring to obtain a cellulose fiber dispersion containing an epoxy resin ( CNF concentration: 7.7% by mass).

Production Example 9 (CNC Dispersion 1) The dried coniferous dried kraft pulp was treated with a coarse grinder and a pin mill to form cotton fibers. This cotton-like fiber was taken out with an absolute dry mass of 100 g, suspended in 2 L of a 64% sulfuric acid aqueous solution, and hydrolyzed at 45 ° C. for 45 minutes.

The suspension liquid thus obtained was filtered, and 10 L of ion-exchanged water was poured therein, and after stirring, they were uniformly dispersed to obtain a dispersion liquid. Next, this dispersion was subjected to a filtration and dehydration step and repeated three times to obtain a dehydrated sheet. Next, the obtained dehydrated flakes were diluted with 10 L of ion-exchanged water, and a 1N sodium hydroxide aqueous solution was added a little at a time while stirring, and the pH was set to about 12. After that, the suspension was filtered and dehydrated, 10 L of ion-exchanged water was added, and the filtration and dehydration step was repeated after stirring.

Next, ion exchanged water was added to the obtained dehydrated sheet to prepare a 2% suspension. This suspension was passed through a wet micronization device ("Ultimaizer" by Sugino Machine Co., Ltd.) at a pressure of 245 MPa for 10 times to obtain an aqueous dispersion of cellulose nanocrystal particles.

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

Next, 50 g of Epiclon 830 DIC (bisphenol F-type epoxy resin) and JER827 Mitsubishi Chemical Corporation (bisphenol A-type epoxy resin) 20g were mixed with ELM100 Sumitomo Chemical Industry (stock) Epoxy resin with amines as precursors: 50 g of triglycidylaminophenol) and 200 g of the acetone dispersion, and after stirring, the acetone was removed by an evaporator to obtain an acid type cellulose fiber dispersion containing an epoxy resin.

Production Example 10 (CNC Dispersion 2) 100 100 g of absorbent cotton (manufactured by White Cross Co., Ltd.) was taken out in absolute dry mass, suspended in 2 L of a 64% sulfuric acid aqueous solution, and hydrolyzed at 45 ° C for 45 minutes.

The suspension liquid thus obtained was filtered, and 10 L of ion-exchanged water was poured therein, and after stirring, they were uniformly dispersed to obtain a dispersion liquid. Next, this dispersion was subjected to a filtration and dehydration step and repeated three times to obtain a dehydrated sheet. Next, the obtained dehydrated flakes were diluted with 10 L of ion-exchanged water, and a 1N sodium hydroxide aqueous solution was added a little at a time while stirring, and the pH was set to about 12. After that, the suspension was filtered and dehydrated, 10 L of ion-exchanged water was added, and the filtration and dehydration step was repeated after stirring.

Next, ion exchanged water was added to the obtained dehydrated sheet to prepare a 2% suspension. This suspension was passed through a wet micronization device ("Ultimaizer" by Sugino Machine Co., Ltd.) at a pressure of 245 MPa for 10 times to obtain an aqueous dispersion of cellulose nanocrystal particles.

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

Next, 50 g of Epiclon 830 DIC (bisphenol F-type epoxy resin) and JER827 Mitsubishi Chemical Corporation (bisphenol A-type epoxy resin) 20g were mixed with ELM100 Sumitomo Chemical Industry (stock) Epoxy resin with amines as precursors: 50 g of triglycidylaminophenol) and 200 g of the acetone dispersion, and after stirring, the acetone was removed by an evaporator to obtain an acid type cellulose fiber dispersion containing an epoxy resin.

According to the descriptions in Tables 42 and 43 below, the components were blended and stirred, and then the dispersion was repeated 6 times using a high-pressure homogenizer Nanovater NVL-ES008 manufactured by Yoshida Machinery Industries to prepare each composition. The numerical values in Tables 42 and 43 represent parts by mass.

[Exudation around the through hole] On a FR-4 copper-laminated laminated board (copper thickness 18μm) of 150mm × 100mm and a thickness of 1.6mm, punch out 3 rows of 10 at a 10mm interval through a 0.8mm diameter drill. For the 30 holes in the row, electroless copper plating was performed in the order of electrolytic copper plating treatment, and a copper plating treatment test substrate with a copper thickness of 25 μm was prepared on the surface of the copper-attached laminated plate. After polishing this test substrate, a plate having a circular opening with a diameter of 0.9 mm was used for the hole portion, and each composition was filled in the through hole by screen printing. Then, after filling, it was placed in a hot-air circulation drying oven. The test piece was obtained by preliminary curing at 120 ° C for 1 hour. The test piece was observed with a magnifying glass, and the bleeding state of the hardened | cured material was evaluated. The evaluation criterion is 0 if the exudation is not seen at all. Although there is no exudation-like exudation, it will be enlarged by the size of the plate as △. Only the resin exudation-like exudation occurs along the polished grinding marks. The exudate was evaluated as ×. The results are shown in Tables 42 and 43.

[Abrasiveness] About a test piece for evaluating the bleeding around the through hole, the abrasiveness was evaluated by polishing (# 320). In the observation with a magnifying glass, the person who completely removes the hardened substance is set to 0 once, and the number of times required to be twice or more is set to ×. The results are shown in Tables 42 and 43.

[Expansion marks on through holes] The test piece for evaluating the abrasiveness was processed in the order of electroless copper plating (Thru-Cup PEA, manufactured by Uemura Industries, Ltd.) and electrolytic copper plating (copper thickness: 10 μm). Then, after passing through the reflow furnace at a peak temperature of 265 ° C three times, the portion on the hole was evaluated visually. Fifteen through-holes have no swelling marks at all, ○, 1 to 5 through-holes have swelling marks at △, and six or more through-holes have swelling marks at x. The results are shown in Tables 42 and 43.

In Examples 7-1 to 7-4, since the CNF dispersion contains thermosetting resins 7-1 to 7-3, the resin components are almost the same as those in the examples and comparative examples. * 7-1) Thermosetting resin 7-1: Epiclon 830 DIC (Bisphenol F-type epoxy resin) 7 * 7-2) Thermosetting resin 7-2: jER827 Mitsubishi Chemical Co., Ltd. ( Bisphenol A epoxy resin) * 7-3) Thermosetting resin 7-3: Sumiepoxy ELM100 manufactured by Sumitomo Chemical Industries, Ltd. (epoxy resin using amines as precursors: triglycidylaminophenol) * 7-4) Thermosetting resin 7-4: Denacol EX-212 Nagase ChemteX (stock) (1,6 hexanediol diglycidyl ether) 7 * 7-5) Hardener 7-1: 2MZA-PW 4 (2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-S-triazine) made by Kokusei Kasei Co., Ltd. 7 * 7-6) Preservative stabilizer 7-1: Cureduct L-07N manufactured by Shikoku Chemical Industry Co., Ltd. (mixture of 5 mass% borate with epoxy resin and varnish resin) 7 * 7-7) inorganic filler 7-1: Softon 1800 Beibei powder Chemical Industry Co., Ltd. (Calcium Carbonate) 7 * 7-8) Defoamer 7-1: KS-66 Shin-Etsu Chemical Industry Co., Ltd.

From the results described in Tables 42 and 43, it was clearly confirmed that by using a curable resin composition in which fine powder such as fine cellulose fibers are dispersed in a resin filler, it is possible to obtain even a component during heating during mounting. Buried materials do not swell on the pores of the buried holes, and do not ooze out the resin component. Even in the grinding step, recessed pore materials are not produced in the pores.

1, 3, 8, 11‧‧‧ conductor pattern

2‧‧‧ core substrate

1a, 4‧‧‧ connecting section

5‧‧‧through hole

6, 9‧‧‧ interlayer insulation

7, 10‧‧‧ interlayer

12‧‧‧solder photoresist layer

101‧‧‧wiring board

102‧‧‧ Substrate

103‧‧‧plated through hole

104‧‧‧Conductor circuit layer

105‧‧‧Pre-cured or hardened resin composition

106‧‧‧Conductor circuit layer

107‧‧‧ Multi-layer printed wiring board with laminated assembly layer on core substrate

108‧‧‧Assembly layer

109‧‧‧conductor circuit layer

110‧‧‧ When forming an assembly layer, a multilayer printed wiring board in which a through hole is formed in a hole and a hardened material of a hardening resin composition is embedded

111‧‧‧ through hole embedded with hardened material of hardening resin composition

112‧‧‧ Residues around the holes that can be generated during the grinding step

113‧‧‧Drilled holes in the grinding step

[Figure 1-1] A graph showing the relationship between the amount of silicon dioxide and fine cellulose powder and the thermal expansion coefficient.图 [Fig. 1-2-1] A graph showing the effect of reducing the thermal expansion rate obtained by using fine cellulose powder in combination.图 [Figure 1-2-2] A graph showing the effect of reducing the thermal expansion coefficient obtained by using fine cellulose powder in combination.图 [Figure 1-3] A graph showing the effect of improving the elongation obtained by using fine cellulose powder in combination. [Fig. 1-4] An explanatory diagram showing a test substrate used in the examples. [Fig. 2-1] A partial cross-sectional view showing a configuration example of a multilayer printed wiring board related to an example of the electronic component of the present invention.图 [Fig. 2-2] An explanatory diagram showing a test substrate used in the examples.图 [Fig. 2-3] It shows other explanatory diagrams of the test substrate used in the examples. [Fig. 2-4] It is another explanatory drawing showing the test substrate used in the examples. [Fig. 3-1] A partial cross-sectional view showing a configuration example of a multilayer printed wiring board related to an example of the electronic component of the present invention.图 [Fig. 3-2] An explanatory diagram showing a test substrate used in the examples. [Fig. 4-1] A partial cross-sectional view showing a configuration example of a multilayer printed wiring board related to an example of the electronic component of the present invention.图 [Fig. 4-2] An explanatory diagram showing a test substrate used in the examples. [Fig. 5-1] A partial cross-sectional view showing a configuration example of a multilayer printed wiring board related to an example of the electronic component of the present invention.图 [Fig. 5-2] An explanatory diagram showing a test substrate used in the examples.图 [Figure 6-1] A graph showing the relationship between the blending amount of silicon dioxide and cellulose nanocrystalline particles and the thermal expansion coefficient.图 [Fig. 6-2-1] A graph showing the effect of reducing the thermal expansion coefficient of cellulose nanocrystal particles in combination.图 [Fig. 6-2-2] A graph showing the effect of reducing the thermal expansion coefficient of cellulose nanocrystal particles in combination.图 [Fig. 6-3] A graph showing the effect of increasing the elongation obtained by combining cellulose nanocrystal particles.图 [Fig. 6-4] An explanatory diagram showing a test substrate used in the examples. [Fig. 7-1] A schematic cross-sectional view showing an example of a method for manufacturing a printed wiring board using the curable resin composition of the present invention. [Fig. 7-2] A partial cross-sectional view showing a configuration example of a multilayer printed wiring board related to an example of the printed wiring board of the present invention. [Fig. 7-3] A partial cross-sectional view showing a configuration example of a multilayer printed wiring board related to an example of the printed wiring board of the present invention.图 [Fig. 7-4] A schematic cross-sectional view explaining the depressions such as the hole portion generated in the polishing step.

Claims (18)

A hardenable resin composition, characterized by comprising a hardening resin of rhenium, a fine powder having at least one atomic size smaller than 100 nm, and a filler other than the fine powder. The curable resin composition according to claim 1, wherein the fine powder is a fine cellulose powder. The curable resin composition according to claim 1, wherein the fine powder is cellulose nanocrystal particles. The curable resin composition according to claim 1, wherein the mixing ratio of the fine powder and the filler other than the fine powder in the full filler is a mass ratio (filler other than the fine powder: fine powder) = 100: (0.04 ~ 30). The curable resin composition according to any one of claims 1 to 4, wherein the curable resin includes a cyclic ether compound having at least one of a naphthalene skeleton and an onion skeleton. The curable resin composition according to any one of claims 1 to 4, wherein the curable resin contains a cyclic ether compound having a dicyclopentadiene skeleton and a phenol resin having a dicyclopentadiene skeleton. At least one species in the group. The curable resin composition according to any one of claims 1 to 4, wherein the curable resin includes a phenoxy resin. The curable resin composition according to any one of claims 1 to 4, wherein the curable resin contains 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. . A dry film comprising a resin layer obtained by applying and drying a curable resin composition as described in claim 1 on a film. A cured product, which is characterized in that the curable resin composition according to claim 1 or the aforementioned resin layer of the dry film according to claim 9 is cured. An electronic component comprising a hardened body as claimed in claim 10. A hardenable resin composition, which is used to fill at least one side of a recessed portion of a printed wiring board and a through hole, and is characterized in that it contains: (A) a fine powder having a size smaller than 100 nm at least once. With (B) thermosetting component. The curable resin composition according to claim 12, further comprising a cyclic ether compound having an amine as a precursor as the (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 (B) thermosetting component. The curable resin composition according to claim 12, further comprising a (C) borate compound. The curable resin composition according to claim 12, further comprising a filler (D) other than the fine powder (A). A hardened product characterized by being hardened by a hardening resin composition according to claim 12. A printed wiring board characterized in that at least one side of a recessed portion and a through hole of the printed wiring board is filled with a hardened material as claimed in claim 17.