KR20190127943A - Curable Resin Compositions, Dry Films, Cured Products, and Electronic Components - Google Patents

Abstract

Curable resin composition which has a low dielectric property and does not damage other characteristics, and can obtain the hardened | cured material which can maintain low thermal expansion coefficient not only in normal temperature but also in the high temperature area | region at the time of component mounting exceeding 200 degreeC, using this Provides dry films, cured products and electronic components. It is a curable resin composition containing the fine powder at least one dimension smaller than 100 nm, and an active ester compound. It is a dry film, hardened | cured material, and an electronic component using this curable resin composition.

Description

Curable Resin Compositions, Dry Films, Cured Products, and Electronic Components

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

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

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

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

Japanese Patent Laid-Open No. 2001-72834

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

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

Then, the objective of this invention is providing the curable resin composition which can obtain the hardened | cured material which can maintain low thermal expansion rate even in the high temperature area at the time of component mounting.

Another object of the present invention is to provide a dry film, a cured product, and an electronic component using the curable resin composition.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that the said subject can be solved by using an active ester compound with the fine powder at least one dimension smaller than 100 nm, and came to solve this invention.

That is, the curable resin composition of this invention is characterized by including the fine powder (henceforth simply called "fine powder" hereafter) smaller than 100 nm in one dimension, and an active ester compound. It is preferable that curable resin composition of this invention contains a filler further.

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

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

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

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

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

For example, in the case of flaky fine powder, the average value of the thickness which is the smallest one dimension is measured, and this average thickness shall be smaller than 100 nm. Specifically, by drawing a diagonal line of the micrograph, and randomly extracting 12 points of fine powder in the vicinity and measuring thickness thereof, and removing the thickest fine powder and the thinnest fine powder, the thickness of the remaining 10 points It is assumed that the average value is smaller than 100 nm.

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

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

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

According to this invention, the curable resin composition which can obtain the hardened | cured material which can maintain low thermal expansion coefficient also in the high temperature area at the time of component mounting can be provided.

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

BRIEF DESCRIPTION OF THE DRAWINGS It is a partial sectional drawing which shows one structural example of the multilayer printed wiring board which concerns on an example of the electronic component of this invention.
2 is an explanatory diagram showing a test substrate used in Examples.

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

Curable resin composition of this invention is characterized by including fine powder and an active ester compound.

With such a structure, a low thermal expansion coefficient can be maintained even in the temperature range at the time of component mounting exceeding 200 degreeC, the dielectric constant and dielectric loss tangent are reduced, and the electronic component which has low dielectric constant characteristics can be obtained.

[Fine powder]

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

The fine powder may be particles having at least one dimension smaller than 100 nm, and the material is not particularly limited. As fine powder, carbon type, such as fullerene, single layer carbon nanotube, and multilayer carbon nanotube, inorganic type, such as silver, gold, iron, nickel, titanium oxide, cerium oxide, zinc oxide, a silica, aluminum hydroxide, etc. are mentioned, for example. Cellulose nanocrystals in which organic matter is processed into nanotubes, nanowires, nanosheets, minerals such as clay, smectite and bentonite, and only crystalline portions are isolated from fine cellulose fibers and cellulose raw materials in which fiber of plants are opened. The fine chitin which opened the chitin obtained from particle | grains, shellfish, etc., the fine chitosan processed by alkali, etc. are mentioned, You may use 2 or more types together. Among these, as hydrophilic fine powder, metal oxide microparticles | fine-particles, such as titanium oxide, metal hydroxide microparticles | fine-particles, such as aluminum hydroxide, mineral microparticles | fine-particles, such as clay, fine cellulose fiber, fine chitin, etc. are mentioned. Among these fine powders, fine cellulose fibers are particularly preferable in view of reinforcing effect and ease of handling. Also preferred are cellulose nanocrystal particles.

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

The compounding quantity of the fine powder in the present invention is preferably 0.04 to 64% by mass, more preferably 0.08 to 30% by mass, and more preferably 0.1 to 10% by mass with respect to the total amount of the composition excluding the solvent. . When the compounding quantity of fine powder is 0.04 mass% or more, the effect of reducing a linear expansion coefficient can be acquired favorably. On the other hand, when it is 64 mass% or less, film forming property improves.

(Fine cellulose fiber)

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The number average fiber diameter of the fine cellulose fiber used for this invention is 3 nm or more, and it is preferable that it is smaller than 100 nm. Since the minimum diameter of a fine cellulose fiber short fiber is 3 nm, when it is less than 3 nm, it cannot manufacture substantially, and when it exceeds 100 nm, it is necessary to add excessively in order to acquire the desired effect of this invention, and film forming property worsens. . In addition, the number average fiber diameter of a fine cellulose fiber can be measured in accordance with the measuring method of the magnitude | size of the fine powder mentioned above.

(Cellulose Nanocrystal Particles)

In the present invention, any of the cellulose nanocrystal particles can be used as long as the cellulose raw material is hydrolyzed with a high concentration of inorganic acid (hydrochloric acid, sulfuric acid, hydrobromic acid, etc.) to isolate only the crystalline portion except for the amorphous portion. Specifically, the cellulose nanocrystal particles can be obtained by subjecting a cellulose raw material to hydrolysis at a concentration of 60 wt% or more with a strong acid having a high concentration of 7 wt% or more, preferably 9 wt% or more, and more preferably sulfuric acid. A crystal that does not contain an amorphous part. By using cellulose nanocrystal particles as fine powder, it is possible to obtain a cured product having a low thermal expansion coefficient even in the temperature range at the time of component mounting exceeding 200 ° C and having excellent properties such as toughness and heat resistance. Excellent curable resin composition can be provided.

The size of the cellulose nanocrystal particles is preferably 3 to 70 nm in average crystal width and 100 to 500 nm in average crystal length, more preferably 3 to 50 nm in average crystal width and 100 to 400 nm in average crystal length. Preferably, it is 3 to 10 nm in average crystal width and 100 to 300 nm in average crystal length. Here, the crystal width means the length of the short side of the particle, and the crystal length means the length of the long side of the particle. Such cellulose nanocrystal particles have a much larger surface area per unit mass than those having a larger width and length than this, and increase the proportion of atoms exposed on the surface. Therefore, it is thought that the reinforcing effect is expressed by taking an interaction in which the cellulose nanocrystal particles attract each other, and the thermal expandability is lowered.

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

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

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

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

Here, the cellulose raw material includes, but is not particularly limited to, pulp for paper, cotton pulp such as cotton linter or cotton lint, hemp, barley, non-wood pulp such as vargas, cellulose isolated from sea urchin and seaweed, and the like. . Among these, paper pulp is preferable from the point of availability, and cotton and sea urchin are preferable at the point which can manufacture CNC which is more excellent in heat resistance.

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

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

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

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

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

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

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

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

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

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

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

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

[Active ester compound]

An active ester compound may be used individually by 1 type, or may use 2 or more types together. Although it does not restrict | limit especially as an active ester compound, What has two or more active ester groups in 1 molecule is preferable. Generally, an active ester compound can be obtained by condensation reaction of one or more of the carboxylic acid compound and the thiocarboxylic acid compound, and one or more of the hydroxy compound and the thiol compound. Examples of the active ester compound include dicyclopentadienyldiphenol ester compounds, bisphenol A diacetate, diphenyl phthalate, diphenyl terephthalate, and bis [4- (methoxycarbonyl) phenyl].

The compounding quantity of an active ester compound becomes like this. Preferably it is 0.5 mass% or more and 80 mass% or less with respect to the total amount of the composition except a solvent, More preferably, it is 1 mass% or more and 40 mass% or less, More preferably, it is 1.5 mass% or more It is 30 mass% or less. When the compounding quantity of the said active ester compound is 0.5 mass% or more, low thermal expansion coefficient can be ensured favorably. On the other hand, when it is 80 mass% or less, sclerosis | hardenability improves.

In this invention, further, curable resins, such as thermosetting resins other than an active ester compound, can be used together as desired.

(Thermosetting resin)

As a thermosetting resin, what is necessary is just resin which hardens by heating and shows electrical insulation, For example, bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol E-type epoxy resin, bisphenol M-type epoxy resin, Bisphenol-type epoxy resins, such as bisphenol P-type epoxy resin and bisphenol Z-type epoxy resin, bisphenol-A novolak-type epoxy resin, phenol novolak-type epoxy resin, novolak-type epoxy resins, such as cresol novolak epoxy resin, and biphenyl type epoxy Resin, biphenyl aralkyl type epoxy resin, arylalkylene type epoxy resin, tetraphenylolethane type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, flu Orene type epoxy resin, glycidyl methacrylate copolymer type epoxy resin, cyclohexyl mal Copolymerized epoxy resin of imide and glycidyl methacrylate, epoxy modified polybutadiene rubber derivative, CTBN modified epoxy resin, trimethylolpropanepolyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl -4,4'- diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris (2,3-epoxy Propyl) isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, phenol novolak resin, cresol novolak resin, bisphenol A novolak resin and other novolak-type phenol resins, unmodified resol Triazine ring-containing resins, such as phenol resins such as phenolic resins, phenoxy resins, urea (urea) resins, melamine resins, and unsaturated resins such as phenolic resins, oil-modified resolphenol resins modified with linseed oil, walnut oil, and the like. On poly Ster resin, bismaleimide resin, diallyl phthalate resin, silicone resin, resin having benzoxazine ring, norbornene-based resin, cyanate resin, isocyanate resin, urethane resin, benzocyclobutene resin, maleimide resin, bismaleim Midtriazine resin, a polyazomethine resin, a thermosetting polyimide, etc. are mentioned.

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

(Carboxyl group-containing resin)

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

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

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

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

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

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

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

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

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

[filler]

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

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

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

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

In this invention, a phenolic compound is used preferably especially. As a phenolic compound, for example, a phenol novolak resin, an alkylphenol novolak resin, a triazine structure containing novolak resin, bisphenol A novolak resin, a dicyclopentadiene type phenol resin, a xyloxic phenol resin, a copna resin, a terpene Known and conventional ones such as phenol compounds such as modified phenol resins and polyvinyl phenols, naphthalene curing agents and fluorene curing agents can be used alone or in combination of two or more thereof. As said phenolic compound, HE-610C, 620C by Air Water Corporation, TD-2131, TD-2106, TD-2093, TD-2091, TD-2090, VH-4150, VH by DIC Corporation -4170, KH-6021, KA-1160, KA-1163, KA-1165, TD-2093-60M, TD-2090-60M, LF-6161, LF-4871, LA-7052, LA-7054, LA-7751 , LA-1356, LA-3018-50P, EXB-9854, SN-170, SN180, SN190, SN475, SN485, SN495, SN375, SN395, JX made by Shinnitetsu Sumikin Kagaku Co., Ltd. DPP, Meiwa Kasei Co., Ltd. HF-1M, HF-3M, HF-4M, H-4, DL-92, MEH-7500, MEH-7600-4H, MEH-7800, MEH- 7851, MEH-7851-4H, MEH-8000H, MEH-8005, Mitsui Chemicals Co., Ltd. XL, XLC, RN, RS, RX etc. are mentioned, However, It is not limited to these. These phenolic compounds can be used individually or in combination of 2 or more types.

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

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

Blue colorant:

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

As dye system, solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 122, solvent blue 136, solvent blue 67, solvent blue 70 may be used. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:

As a green coloring agent, there exist phthalocyanine series and anthraquinone system similarly, 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, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:

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

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

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

Condensed Azo System: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

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

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

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

Red colorant:

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

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

Disazo meter: Pigment Red 37, 38, 41.

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

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

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

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

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

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

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

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

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

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

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

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

The curable resin composition of this invention may be used for dry film forming, or may be used as a liquid phase. Moreover, curable resin composition of this invention can also be used as a prepreg coated and impregnated and semi-hardened to sheet-like fibrous base materials, such as a nonwoven fabric of glass cloth, glass, and aramid. In the case of using as a liquid, it may be one-liquid or two-liquid or more. As a two-component composition, it is good also as a composition which divided the fine cellulose fiber and the active ester compound, for example.

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

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

After forming the resin layer containing curable resin composition of this invention on a carrier film, the cover film which can be peeled off is further laminated | stacked on the surface of a resin layer in order to prevent sticking to the surface of a resin layer. It is desirable to. As a peelable cover film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, the surface-treated paper, etc. can be used, for example. As a cover film, when peeling a cover film, what is necessary is just the adhesive force between a resin layer and a thing smaller than the adhesive force of a resin layer and a carrier film.

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

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

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

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

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

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

Example

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

[Production of Fine Cellulose Fibers]

Preparation Example 1 (CNF1)

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

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

Preparation Example 2 (CNF2)

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

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

Preparation Example 3 (CNF3)

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

[Production of Cellulose Nanocrystal Particles]

Preparation Example 4 (CNC1)

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

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

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

Subsequently, after solvent substitution with acetone, solvent substitution was carried out as DMF, and the DMF dispersion liquid (solid content concentration 5.0 mass%) of the cellulose nanocrystal particle swelled was obtained. As a result of observing and measuring the cellulose nanocrystal particle in the obtained dispersion liquid by AFM, the average crystal width was 10 nm and the average crystal length was 200 nm.

Preparation Example 5 (CNC2)

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

According to the description of the following Tables 1-4, after mixing and stirring each component, it was made to disperse | distribute 6 times repeatedly using the high-pressure homogenizer Nanovater NVL-ES008 of Yoshida Kikai Kogyo Co., Ltd., and each composition was manufactured. In addition, the numerical value of Tables 1-4 shows a mass part.

[Coefficient of Thermal Expansion]

Each composition was apply | coated to the PET film with a thickness of 38 micrometers with the applicator of a gap of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Then, it crimped | bonded for 60 second on 60 degreeC and the pressure of 0.5 MPa on the copper foil of thickness 18micrometer with a vacuum laminator, laminated the resin layer of each composition, and peeled off the PET film. Subsequently, it heated and hardened | cured by 180 degreeC 30 minutes in a hot air circulation type drying furnace, the copper foil was peeled off, and the sample of the cured film was obtained. The produced thermal expansion sample was cut into 3 mm width x 30 mm length. The test piece was heated to 5 ° C./min to 20 to 250 ° C. under a tension mode of 16 mm, a load of 30 mN, and a nitrogen atmosphere using a TMA (Thermomechanical Analysis) Q400 manufactured by T-A Instruments Inc., followed by 250 to 20 ° C. It was measured by lowering the temperature to 5 ℃ / min. At the time of temperature reduction, the thermal expansion coefficient (ppm / K) in 25 degreeC and 200 degreeC was calculated | required. In addition, the temperature of the sharp change point of thermal expansion rate was made into Tg (glass transition point). The results are shown in Tables 1-4.

[Relative dielectric constant, dielectric loss tangent]

Each composition was apply | coated to the PET film of thickness 38micrometer with the applicator of 200 micrometers, and it dried in the hot air circulation type drying furnace for 90 degreeC for 20 minutes, and obtained the dry film which has a resin layer of each composition. Thereafter, the electrolytic copper foil having a thickness of 18 µm was pressed against the substrate fixed with a gloss surface on a FR-4 copper clad laminate having a thickness of 1.6 mm with a vacuum laminator for 60 seconds under a vacuum laminator at a pressure of 0.5 MPa for 60 seconds. The resin layer was laminated, the PET film was peeled off, and heated at 180 ° C. for 30 minutes in a hot air circulation drying furnace to cure. And the fixed tape was peeled off, the electrolytic copper foil was peeled off, it cut out to the magnitude | size of 1.7 mm x 100 mm, and it was set as the sample for evaluation. The measurement was performed with the network analyzer E-507 by Keysight Technologies, using the cavity resonator (5GHz) by Kanto Den-shi Ohyo Kaihatsu. In the evaluation of the relative dielectric constant, the average value measured three times was less than 2.8, and ◎, 2.8 or more, and less than 3.0 were defined as x and 3.0 or more. The evaluation of the dielectric loss tangent was that the average value measured three times was less than 0.02, and that the average value was 0.02 or more. Each result is shown to Tables 1-4.

[Solder heat resistance]

In a 150 mm × 95 mm, 1.6 mm thick FR-4 copper clad laminate, each composition was formed into a full-side solid pattern by 80 mesh Tetron bias plate screen printing, and dried in a hot air circulation drying furnace for 30 minutes at 80 ° C., followed by 180 It heated and hardened 30 degreeC, and obtained the test piece. The rosin type flux was apply | coated to the hardened | cured material side of the composition of this test piece, it flowed into the 260 degreeC solder layer for 60 second, and it wash | cleaned with propylene glycol monomethyl ether acetate, and then it wash | cleaned with ethanol. About the test piece, swelling and peeling of the coating film, and the change of the surface state were observed visually. The thing which showed abnormality by swelling and peeling, surface melt | dissolution, softening, etc. in a coating film was evaluated as x and what was invisible. The evaluation results are shown in Tables 1 to 4.

[Insulation]

Each composition was apply | coated to the PET film with a thickness of 38 micrometers with the applicator of a gap of 120 micrometers, and it dried at 90 degreeC for 10 minutes in the hot air circulation type drying furnace, and obtained the dry film which has a resin layer of each composition. Subsequently, each composition was pressed for 60 seconds under a condition of 60 ° C. and a pressure of 0.5 MPa using a vacuum laminator on an A coupon of IPC MULTI-PURPOSE TEST BOARD B-25 formed on a 1.6 mm thick FR-4 substrate with a thickness of 35 μm copper. The resin layer was laminated, the PET film was peeled off, and heated at 180 ° C. for 30 minutes in a hot air circulation drying furnace to cure. Subsequently, the lower end of the IPC MULTI-PURPOSE TEST BOARD B-25 was cut to form an electrically independent terminal (cut at the dotted line in FIG. 2). Then, a bias of 500 V DC was applied so that the upper portion of the A coupon was the negative electrode and the lower portion was the positive electrode, and the insulation resistance value was measured. Evaluation evaluated that the insulation resistance value was 100 GΩ or more, and that the insulation resistance value was less than 100 GΩ. The results are shown in Tables 1-4.

* 1) Thermosetting resin 1: cyclohexanone varnish (cyclic ether compound having a dicyclopentadiene skeleton) of 50% by mass of epiclon HP-7200 solid content

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

* 3) Thermosetting resin 3: Epiclone 830 DIC Corporation

* 4) Thermosetting resin 4: JER827 Mitsubishi Chemical Corporation

* 5) Thermosetting resin 5: Bisphenol A diacetate Tokyo Kasei Kogyo Co., Ltd. product (active ester)

* 6) Thermosetting resin 6: Epiclone HPC-8000-65T DIC Corporation make (65 mass% of active ester solids)

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

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

* 9) Filler 1: Admafine SO-C2 Co., Ltd. product (silica) mean particle size 0.4-0.6 micrometer

* 10) Organic Solvent 1: Dimethylformamide

* 11) Defoamer 1: BYK-352 Big Chemie Japan Co., Ltd. product

* 12) Filler 2: B-30 Barium sulfate manufactured by Kagaku Kagaku Kogyo Co., Ltd.

* 13) Filler 3: DAW-07 Tenka Co., Ltd. Alumina

* 14) Dispersant 1: DISPERBYK-111 by Big Chemistry

As evident from the results shown in Tables 1 to 4, by containing fine powders such as fine cellulose fibers and cellulose nanocrystal particles and active ester compounds, low thermal expansion coefficients are maintained not only at normal temperature but also at high temperatures when mounting parts. It was confirmed that curable resin compositions having low dielectric properties can be obtained. Moreover, from the evaluation result of solder heat resistance, it was confirmed that each composition of the Example was excellent in heat resistance and chemical-resistance, and can be used as a composition for wiring boards.

1, 3, 8, 11 conductor pattern
2 core board
1a, 4 connections
5 through hole
6, 9 interlayer insulation layer
7, 10 vias
12 solder resist layer

Claims (5)

Curable resin composition characterized by including at least one dimension fine powder smaller than 100 nm and an active ester compound. The curable resin composition according to claim 1, further comprising a filler. The curable resin composition of Claim 1 has a resin layer apply | coated and dried on a film, The dry film characterized by the above-mentioned. The said resin layer of the curable resin composition of Claim 1 or the dry film of Claim 3 is hardened | cured, The hardened | cured material characterized by the above-mentioned. The hardened | cured material of Claim 4 is provided, The electronic component characterized by the above-mentioned.

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