KR20190050980A - Curable resin composition for printed wiring board, dry film, cured product and printed wiring board - Google Patents

Abstract

A curable resin composition, a dry film, a cured product and a printed wiring board for a printed wiring board which are low in thermal expansion and which can obtain a cured product having good adhesion to a metal conductor. Microcrystalline cellulose fibers obtained by modifying a carboxyl group of a microcellulose fiber having a carboxyl group with at least one of an amine compound and a quaternary ammonium compound to be hydrophobic, and a curable resin. The average fiber diameter of the microcellulose fibers having a carboxyl group is 0.1 nm or more and 200 nm or less, the average fiber length is 600 nm or less, and the average aspect ratio is 1 or more and 200 or less.

Description

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

The present invention relates to a curable resin composition for a printed wiring board (hereinafter, simply referred to as a " curable resin composition ") containing hydrophobized microcellulose fibers, a dry film, a cured product and a printed wiring board.

The printed wiring board is used for connecting and fixing the electronic parts by wiring the conductor to the insulating substrate. Depending on the application, the insulating layer and the conductor layer may be multilayered or a flexible insulating substrate may be used. It is an important component. The printed wiring board is also used for a semiconductor package, and the curable resin composition for a printed wiring board and the dry film are used as a wiring board or an outer layer after semiconductor mounting.

2. Description of the Related Art In recent years, with the miniaturization of electronic devices, there has been a demand for higher density wiring for printed wiring boards. For ensuring the reliability of wiring and component connecting parts, the materials of printed wiring boards are required to have low thermal expansion properties.

As a method of achieving low thermal expansion, for example, Patent Documents 1 and 2 propose a method using a material in which microcellulose fibers are dispersed in a composition.

Japanese Patent Application Laid-Open No. 2011-001559 Japanese Patent Application Laid-Open No. 121-119470

However, in the materials described in Patent Documents 1 and 2, there is a problem that reliability is lowered such that the adhesion of the metal conductor is deteriorated.

Therefore, an object of the present invention is to provide a curable resin composition for a printed wiring board, a dry film, a cured product and a printed wiring board which can obtain a cured product having a low thermal expansion property and good adhesion to a metal conductor.

As a result of intensive investigations, the inventors of the present invention have found that a microcellulose fiber having a carboxyl group having an average fiber diameter in a specific range, an average fiber length of not more than a specific value and an aspect ratio indicating a ratio of an average fiber diameter to an average fiber length, The above problems can be solved, and the present invention has been accomplished.

That is, the curable resin composition for a printed wiring board according to the present invention is a curable resin composition for a printed wiring board, which comprises a microcellulose fiber obtained by hydrophobing a corresponding carboxyl group of a microcellulose fiber having a carboxyl group with at least one of an amine compound and a quaternary ammonium compound, , Wherein the resin composition

Wherein the microcellulose fibers having carboxyl groups have an average fiber diameter of 0.1 nm or more and 200 nm or less, an average fiber length of 600 nm or less, and an average aspect ratio of 1 or more and 200 or less.

The resin composition of the present invention preferably further comprises silica. The resin composition of the present invention preferably contains at least one of a thermosetting resin and a photo-curable resin as the curable resin.

The dry film of the present invention is characterized by having a resin layer formed by applying and drying the curable resin composition for a printed wiring board on a film.

The cured product of the present invention is characterized in that the curable resin composition for a printed wiring board or the resin layer of the dry film is cured.

The printed wiring board of the present invention is characterized by comprising the cured product.

According to the present invention, it becomes possible to realize a curable resin composition, a dry film, a cured product and a printed wiring board for a printed wiring board which can obtain a cured product having low thermal expansion and good adhesion to a metal conductor.

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

The curable resin composition for a printed wiring board of the present invention comprises a microcellulose fiber obtained by hydrophobing a carboxyl group of a microcellulose fiber having a carboxyl group with at least one of an amine compound and a quaternary ammonium compound and hydrophobizing the microcellulose fiber, (Average fiber length / average fiber diameter) of not less than 1 and not more than 200 are used as the microcellulose fibers having a carboxyl group and having an average fiber diameter of not less than 0.1 nm and not more than 200 nm, an average fiber length of not more than 600 nm and an average aspect ratio .

Here, the microcellulose fibers having a carboxyl group have an average fiber diameter of 0.1 nm or more and 200 nm or less, an average fiber length of 600 nm or less and an average aspect ratio of 1 or more and 200 or less, but the carboxyl groups of the microcellular cellulose fibers having a carboxyl group are modified The fine cellulosic fibers obtained by hydrophobicity also have an average fiber diameter of 0.1 nm or more and 200 nm or less, an average fiber length of 600 nm or less, and an average aspect ratio of 1 or more and 200 or less.

Hereinafter, the microcellulose fiber having a carboxyl group is also referred to as a carboxyl group-containing microcellulose fiber, and the microcellulose fiber obtained by hydrophobing the carboxyl group of the carboxyl group-containing microcellulose fiber is also referred to as hydrophobic microcellulose fiber.

Conventionally, hydrophobic treatments such as binding of various water-soluble groups to the microcellular cellulose fibers having a carboxyl group having an average aspect ratio of about 300 have been carried out. Such microcellular cellulose fibers are low in thermal expansion property but have low adhesion to metal conductors .

However, the inventors of the present invention found that when a hydrophobic treatment is applied to a microcellulose fiber containing a carboxyl group having an average aspect ratio of 1 or more and 200 or less, and a composition containing a curable resin, the cured product obtained from the composition maintains low thermal expansion, Is also excellent.

The detailed reason why such effects are exhibited is unclear, but the carboxyl group-containing microcellulose fibers having an average aspect ratio in the above range are short fibers in which the weak portions existing in the natural cellulose fibers, for example, amorphous regions are cut, It is presumed that a short fiber and a low thermal expansion property can be maintained in that the distribution ratio of the crystal region increases.

In addition, since the obtained hydrophobic microcellulose fibers have a short fiber length, the dispersibility in the resin composition is improved, and the effect as a filler is sufficiently exhibited. Therefore, it is considered that the adhesion to the metal conductor is excellent do.

The curable resin composition of the present invention is suitably used for forming an insulating layer of a printed wiring board and is suitably used for forming a surface protective layer such as a core layer of a printed wiring board, an interlayer insulating layer, a solder resist, or the like .

Examples of the curable resin composition of the present invention include a thermosetting resin composition containing a thermosetting resin, a photocurable resin composition containing a photocurable resin, a photocurable thermosetting resin composition containing a photocurable resin and a thermosetting resin have.

[Hydrophobic microcellulose fiber]

The hydrophobic microcellulose fiber is obtained by modifying the carboxyl group of the carboxyl group-containing microcellulose fiber with at least one of an amine compound and a quaternary ammonium compound to be hydrophobized and can be obtained as follows.

Examples of the natural cellulose fiber as a raw material include wood pulp such as softwood pulp and hardwood pulp; Cotton pulp such as cotton linter, cotton lint; Pulp based on non-wood such as straw pulp and bagasse pulp; Bacterial cellulose, etc. One of these may be used singly or two or more of them may be used in combination.

The raw material is mainly composed of cellulose, hemicellulose and lignin. The content of lignin is usually about 0 to 40 mass%, particularly about 0 to 10 mass%. With respect to these raw materials, the lignin amount can be adjusted by performing lignin removal or bleaching treatment if necessary. Further, the lignin content can be measured by the Klason method.

In the cell walls of plants, cellulosic molecules are not monomolecular but are regularly aggregated to form microfibrils having crystallizations in which dozens are aggregated, which is the basic skeleton material of plants. Therefore, in order to produce microcellulose fibers from the raw materials, the raw materials can be untangled to nano-size by subjecting the raw materials to a treatment with a high-temperature or high-pressure steam treatment, a treatment with a phosphate or the like.

Further, by oxidizing the natural cellulose fiber with a carboxyl group at the C6 position in the glucopyranose ring of natural cellulose by oxidation treatment (for example, oxidation treatment using TEMPO described later), carboxyl group Containing cellulose fibers can be obtained. By carrying out this treatment, the cellulose fibers can be released to a nano-size with a relatively weak shear force.

In addition, the hydrophobic microcellulose fiber can be obtained by modifying the carboxyl group of the carboxyl group-containing cellulose fiber with at least one of an amine compound and a quaternary ammonium compound to hydrophobize the carboxyl group-containing cellulose fiber.

Hereinafter, a method for producing hydrophobic microcellulose fibers used in the present invention will be described in detail.

(Slurrying step)

First, a slurry in which natural cellulose fibers are dispersed in water is prepared. Water is added to the slurry in an amount of about 10 to 1000 times (mass basis) relative to the natural cellulose fiber to be the raw material (the mass of the natural cellulose fiber obtained by heating and drying for 30 minutes at 150 캜 on the basis of absolute drying) . The natural cellulose fiber may be subjected to a treatment for increasing the surface area such as defatting. The cellulose I-form crystallinity of commercially available pulp is usually 80% or more.

(Oxidation treatment step)

Subsequently, the natural cellulose fibers are subjected to an oxidation treatment in the presence of an oxidizing agent such as an N-oxyl compound to obtain a carboxyl group-containing cellulose fiber (hereinafter, simply referred to as "oxidation treatment").

As the N-oxyl compound, at least one heterocyclic N-oxyl compound selected from a piperidineoxyl compound having an alkyl group having 1 or 2 carbon atoms, a pyrrolidineoxyl compound, an imidazoline oxyl compound and an azadimantane compound desirable. Among them, piperidineoxyl compounds having an alkyl group having 1 or 2 carbon atoms are preferable from the viewpoint of reactivity, and 2,2,6,6-tetraalkylpiperidine-1-oxyl (TEMPO), 4-hydroxy -2,2,6,6-tetraalkylpiperidine-1-oxyl, 4-alkoxy-2,2,6,6-tetraalkylpiperidine-1-oxyl, 4- benzoyloxy- Di-tert-alkylnitroxyl compounds such as 6,6-tetraalkylpiperidine-1-oxyl and 4-amino-2,2,6,6-tetraalkylpiperidine-1-oxyl, -TEMPO, 4-carboxy-TEMPO, 4-phosphonoxy-TEMPO, and the like. Among these piperidineoxyl compounds, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidine- Oxyl and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl are more preferable, and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) Is more preferable.

The amount of the N-oxyl compound may be a catalytic amount, and is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 9 parts by mass, more preferably 0.1 to 8 parts by mass, relative to 100 parts by mass of the natural cellulose fiber (absolute drying standard) More preferably 0.5 to 5 parts by mass.

In the oxidation treatment of the natural cellulose fibers, an oxidizing agent other than the N-oxyl compound can be used. From the viewpoints of the solubility and the reaction rate when the solvent is adjusted to the alkaline region, the oxidizing agent may be oxygen or air, peroxide; Halogen, hypohalous acid, halogenated acid, perhalogen acid and alkali metal or alkaline earth metal salts thereof; Halogen oxides, nitrogen oxides and the like. Among them, an alkali metal hypochlorite is preferable, and specifically sodium hypochlorite and sodium hypobromite are exemplified. The amount of the oxidizing agent to be used can be selected according to the substitution degree (degree of oxidation) of the carboxyl group of the natural cellulose fiber and is not uniformly determined because the oxidation reaction yield varies depending on the reaction conditions. However, ) Is preferably in the range of about 1 to 100 parts by mass per 100 parts by mass.

Further, in order to carry out the oxidation reaction more efficiently, bromides such as sodium bromide and potassium bromide, iodides such as sodium iodide and potassium iodide and the like can be used as the co-catalyst. The amount of the cocatalyst may be an effective amount capable of exerting its function, and there is no particular limitation.

The reaction temperature in the oxidation treatment is preferably 50 占 폚 or lower, more preferably 40 占 폚 or lower, still more preferably 20 占 폚 or lower, from the viewpoints of selectivity of reaction and suppression of side reactions, 5 ° C or higher.

The pH of the reaction system is preferably adjusted to the nature of the oxidizing agent. For example, when sodium hypochlorite is used as the oxidizing agent, the pH of the reaction system is preferably alkaline, preferably pH 7 to 13, 13 is more preferable. The reaction time is preferably 1 to 240 minutes.

By carrying out the oxidation treatment, a carboxyl group-containing cellulose fiber having a carboxyl group content of preferably 0.1 mmol / g or more can be obtained.

(Purification process)

The carboxyl group-containing cellulose fibers obtained in the oxidation treatment step include N-oxyl compounds such as TEMPO used as a catalyst and by-products. The following steps may be carried out as it is, but purification may be carried out to obtain carboxyl group-containing cellulose fibers having high purity. As the purification method, an optimum method can be adopted depending on the kind of the solvent in the oxidation reaction, the degree of oxidation of the product, and the degree of purification. For example, reprecipitation using water as a good solvent, reprecipitation using methanol, ethanol, acetone or the like as a poor solvent, extraction of TEMPO with a solvent that is phase-separated from water such as hexane, purification by ion exchange of salt, .

(Finishing step)

Then, a step of making the carboxyl group-containing cellulose fibers obtained after the purification step is made fine. In the micronization step, it is preferable that the cellulose group-containing cellulose fibers subjected to the purification step are dispersed in a solvent and subjected to fineness treatment. By carrying out this refining step, microcellulose fibers having an average aspect ratio in the above range can be obtained.

As the solvent for the dispersion medium, in addition to water, alcohols having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, such as methanol, ethanol and propanol; Ketones having 3 to 6 carbon atoms such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Saturated or unsaturated hydrocarbons having 1 to 6 carbon atoms; Aromatic hydrocarbons such as benzene and toluene; Halogenated hydrocarbons such as methylene chloride and chloroform; Lower alkyl ethers having 2 to 5 carbon atoms; And polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and diesters of succinic acid and triethylene glycol monomethyl ether. These solvents may be used alone or in admixture of two or more. In view of the operability of the finely divided treatment, water, an alcohol having 1 to 6 carbon atoms, a ketone having 3 to 6 carbon atoms, a lower alkyl ether having 2 to 5 carbon atoms, Polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and succinic acid methyltriglycol diester are preferable, and water is more preferable from the viewpoint of environmental load reduction. The amount of the solvent to be used is not particularly limited and may be an effective amount capable of dispersing the carboxyl group-containing cellulose fibers. The solvent may be used in an amount of preferably 1 to 500 times by mass, more preferably 2 to 200 times by mass with respect to the carboxyl group-containing cellulose fibers .

As the apparatus used in the fineness treatment, known dispersing apparatuses are suitably used. For example, a grinder, a cutter mill, a ball mill, a jet mill, a single screw extruder, a twin screw extruder, an ultrasonic stirrer, a domestic screw kneader, and the like can be used as a stirrer, a breaker, a low pressure homogenizer, a high pressure homogenizer, The solid content concentration of the reactant fiber in the fineness treatment is preferably 50 mass% or less.

Further, in the present invention, at least one process selected from a biochemical process, a chemical process, and a mechanical process may be further performed before the above-described miniaturization process. Specifically, there are treatment methods such as acid hydrolysis, hydrolysis, oxidative decomposition, pulverization, enzymatic treatment, UV treatment, electron beam treatment, etc. By these treatments, shortening of the cellulose fibers is achieved, So that the average aspect ratio is included within the above range. Examples of the treatment include, for example, a method of refluxing carboxyl group-containing cellulose fibers subjected to a purification process to an acid. The kind of the acid and its concentration are not particularly limited. For example, a method of heating an aqueous dispersion of a carboxyl group-containing cellulose fiber having a hydrochloric acid concentration of 0.1 to 10 M by adding concentrated hydrochloric acid is exemplified.

As the form of the obtained fine cellulosic fibers, there may be used a suspension (a colorless transparent or opaque liquid for purpose), or a dried powdery form (in the form of a powder in which fine cellulose fibers are agglomerated) whose cellulosic particles It does not mean that you can do it). In the case of a suspension, the water may be used alone as the dispersion medium, or a mixed solvent of water and other organic solvents (for example, alcohols such as ethanol), a surfactant, an acid, and a base may be used.

As described above, the hydroxyl group at the C6 position of the cellulose constituting unit is selectively oxidized to a carboxyl group via an aldehyde group to have a carboxyl group content of 0.1 mmol / g or more, an average fiber diameter of 0.1 to 200 nm, an average fiber length of 600 nm Hereinafter, micronized cellulose having an average aspect ratio of 1 or more and 200 or less, preferably microcellulose fibers having a crystallinity of 30% or more can be obtained.

[Average fiber diameter, average fiber length and average aspect ratio of microcellulose fibers]

The average fiber diameter, average fiber length and average aspect ratio of the carboxyl group-containing microcellulose fibers can be measured as follows.

Water was added to the carboxyl group-containing microcellulose fiber to prepare a dispersion having a concentration of 0.0001% by mass, and the dispersion was dropped on a mica (mica) and dried. As an observation sample, an atomic force microscope (AFM, Nanoscope III Tapping mode AFM, manufactured by Digital Instruments, and a probe using Point Probe (NCH) manufactured by Nanosensors), and the fiber height of the microcellulose fibers in the observation sample is measured. At this time, in the microscopic image confirming the microcellulose fibers, five or more microcellulose fibers are extracted and the average fiber diameter is calculated from the height of the fibers. Further, the average fiber length is calculated from the distance in the fiber direction. The average aspect ratio is calculated from the average fiber length / average fiber diameter.

In the present invention, the average fiber diameter of the carboxyl group-containing microcellulose fibers is 0.1 nm or more and 200 nm or less, preferably 1 nm or more and 100 nm or less, more preferably 2 nm or more and 50 nm or less, and further preferably 2.5 nm or more and 20 nm or less. When the average fiber diameter is less than 0.1 nm, it is difficult to produce. When the average fiber diameter exceeds 200 nm, a cured product having good adhesion to the conductor of the printed wiring board can not be obtained.

The average fiber length of the carboxyl group-containing microcellulose fibers is 600 nm or less, preferably 50 nm or more and 600 nm or less, more preferably 100 nm or more and 500 nm or less, and further preferably 150 nm or more and 500 nm or less. When the average fiber length exceeds 600 nm, dispersion becomes difficult when the composition is used.

The average aspect ratio of the carboxyl group-containing microcellulose fibers is 1 or more and 200 or less, preferably 5 or more and 180 or less, more preferably 9 or more and 170 or less, particularly preferably 9 or more and 100 or less. If the average aspect ratio is less than 1, it is difficult to produce. If the average aspect ratio exceeds 200, a cured product having good adhesion to the metal conductor can not be obtained. When the average aspect ratio is 200 or less, the adhesion between the metal conductor and the cured product is improved. As the average aspect ratio is decreased, the adhesion between the metal conductor and the cured product is excellent, and the viscosity of the composition can be lowered.

In the present invention, microcellulose fibers obtained by modifying the carboxyl group and hydrophobizing the cellulose are used. That is, hydrophobic microcellulose fibers obtained by modifying a microcellulose fiber having a carboxyl group with an amine compound or a quaternary ammonium compound are used.

Hereinafter, the hydrophobic microcellulose fiber will be described.

In the microcellulose fiber formed by hydrophobizing the carboxyl group of the carboxyl group-containing microcellulose fiber, the water-soluble group is bonded to the cellulose main chain through either or both of the amide bond and the amine salt.

The alkyl group may be any functional group that bonds through either or both of the amide bond and the amine salt. For example, a hydrocarbon group having 1 carbon atom or a saturated or unsaturated straight or branched hydrocarbon group having 2 to 30 carbon atoms may be used. . Specific examples thereof include the following hydrocarbon groups.

Hydrocarbon group having 1 carbon atom: methyl group.

A saturated straight chain hydrocarbon group having 2 to 30 carbon atoms: an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, an octadecyl group, a docosyl group and an octacosyl group.

Unsaturated straight chain hydrocarbon group having 2 to 30 carbon atoms: oleyl group, myristyl group, palmitoleyl group, linoleyl group, linolenyl group, eicosanyl group.

Saturated branched hydrocarbon groups of 2 to 30 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, t-pentyl, isohexyl, Butyl group, ethyl butyl group.

The number of carbon atoms of the saturated or unsaturated straight-chain or branched hydrocarbon group is arbitrarily selected depending on the combination with the curable resin, but is preferably 1 or more, especially 3 or more, more preferably 10 or more, further preferably 30 or less, Among them, it is preferable that it is 18 or less. For example, it is preferably 1 or more and 30 or less, more preferably 3 or more and 20 or less, still more preferably 10 or more and 18 or less. When the number of carbon atoms is within the above-mentioned range, the microcellulose fibers and the curable resin become uniformly mixed, and good physical properties such as a low coefficient of linear thermal expansion can be obtained.

Specific examples of the amine having a saturated or unsaturated straight-chain or branched hydrocarbon group include methylamine, ethylamine, propylamine, isopropylamine, butylamine, hexylamine, octylamine, Decylamine, dodecylamine, octadecylamine, oleylamine, and other monoalkylamines. Examples of secondary amines include dialkylamines such as dimethylamine, diethylamine, dibutylamine and dioctadecylamine.

The amine having an aromatic hydrocarbon group may have a total carbon number of 6 to 20, and may be either a primary amine or a secondary amine, but a primary amine is preferable from the viewpoint of reactivity with a carboxyl group. The number of aromatic hydrocarbon groups in the amine may be either one or two, provided that the total number of carbon atoms is 6 to 20, but is preferably one.

Examples of the amine having an aromatic hydrocarbon group include an amine having an aryl group and an amine having an aralkyl group, and from the viewpoint of compatibility with a resin, an amine having an aryl group is preferable.

Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group and a triphenyl group, and these may be used alone or in combination of two or more. Among them, a phenyl group, a naphthyl group and a biphenyl group are preferable from the viewpoint of compatibility with a resin, and a phenyl group is more preferable.

Specific examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylpentyl group, a phenylhexyl group and a phenylheptyl group, and these may be used alone or in combination of two or more. Among them, a benzyl group, a phenethyl group, a phenylpropyl group, a phenylpentyl group and a phenylhexyl group are preferable, and a benzyl group, a phenethyl group, a phenylpropyl group and a phenylpentyl group are more preferable from the viewpoint of compatibility with a resin.

The aryl group and the aralkyl group may have a substituent. Examples of the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec- An alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a butyl group, a butyl group, Examples of the alkyl group having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, An alkoxy group; An alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, An alkoxycarbonyl group of 6 to 6 carbon atoms; A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; An acyl group having 1 to 6 carbon atoms, an aralkyl group, and an aralkyloxy group.

Specific examples of the amines having an aromatic hydrocarbon group include amines having an aryl group such as aniline, toluylamine, 4-biphenylyl amine, diphenylamine, 2-aminonaphthalene, p-terphenylamine, , And 2-aminoanthraquinone. Of these, aniline, toluylamine, 4-biphenylyl amine, diphenylamine and 2-aminonaphthalene are preferable from the standpoint of compatibility with resins, and aniline is more preferable. Examples of the amine having an aralkyl group include benzylamine, phenethylamine, 3-phenylpropylamine, 5-phenylpentylamine, 6-phenylhexylamine, 7-phenylheptylamine and 8-phenyloctylamine. Of these, benzylamine, phenethylamine, 3-phenylpropylamine, 5-phenylpentylamine, 6-phenylhexylamine, and 7-phenylheptylamine are preferable from the same viewpoint, and benzylamine, phenethylamine, 3-phenyl Propylamine, 5-phenylpentylamine and 6-phenylhexylamine are more preferable, and benzylamine, phenethylamine, 3-phenylpropylamine and 5-phenylpentylamine are more preferable. The amine having an aromatic hydrocarbon group used in the present invention may be produced according to a known method or may be a commercially available product.

In addition, an amine having a hydrophilic group such as an amine, a hydroxyethyl group or a hydroxypropyl group obtained by aminating an end of a hydroxyl group with a desired amount of ethylene oxide or propylene oxide added to the propylene glycol alkyl ether, or an amine having a hydrophilic group such as ethylene glycol, propylene glycol , Polyether amines having a polyester chain such as lactide and caprolactone, and amines having alicyclic hydrocarbons such as polyester amines, cyclopentyl groups and cyclohexyl groups, as well as hydrophobic microcellulose used in the present invention And is suitably used as a compound which binds to fibers through either or both of an amide bond and an amine salt.

Examples of the quaternary ammonium compound for modifying the carboxyl group of the hydrophobic microcellulose fiber to form an amine salt include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, Tetraethyl ammonium chloride, tetrabutyl ammonium chloride, lauryl trimethyl ammonium chloride, dilauryl dimethyl chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, cetyl trimethyl ammonium chloride and alkyl benzyl dimethyl ammonium chloride. Among them, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide are preferable from the viewpoint of ease of modification into a carboxyl group.

The amount of hydrophobic microcellulose fiber to be added in the curable resin composition of the present invention is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more (based on 100 parts by mass of the total amount of the curable resin) 20 parts by mass or less, and more preferably 2 parts by mass or more and 10 parts by mass or less. When the addition amount is 0.1 parts by mass or more, the thermal expansion property is lowered, and when it is 30 parts by mass or less, the balance between the low thermal expansion property and the adhesion property of the metal conductor is excellent.

(Method for Modifying the Carboxyl Group of Microcellulose Fibers)

As the method for modifying the carboxyl group of the microcellulose fiber in the present invention, the following may be mentioned.

As a first method, there can be mentioned a method in which an amine compound having a carboxyl group-containing microcellulose fiber and a water-soluble group is mixed in a solvent to form a salt.

The amount of the amine compound to be used can be determined according to the binding amount of the desired amine salt in the hydrophobic microcellulose fiber, but the amount of the amino group is preferably 0.1 mol or more, more preferably 0.1 mol or more per mol of the carboxyl group contained in the carboxyl group- Is preferably not less than 0.5 mol, more preferably not less than 0.7 mol, still more preferably not less than 1 mol, and preferably not more than 50 mol, more preferably not more than 20 mol, still more preferably not more than 10 mol, from the viewpoint of product purity use. Amines in the above range may be used in a salt forming step at one time or may be used in a salt forming step by dividing.

As the solvent, it is preferable to select a solvent in which the amine compound to be used is dissolved. Examples of the solvent include ethanol, isopropanol (IPA), N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO) There may be mentioned dimethyl acetamide, tetrahydrofuran (THF), diester of succinic acid and triethylene glycol monomethyl ether, acetone, methyl ethyl ketone (MEK), acetonitrile, dichloromethane, chloroform, toluene, May be used alone or in combination of two or more. Among these polar solvents, succinic acid and diesters of triethylene glycol monomethyl ether, ethanol and DMF are preferable.

The temperature at the time of mixing is preferably 0 占 폚 or higher, more preferably 5 占 폚 or higher, and still more preferably 10 占 폚 or higher. From the standpoint of coloration of the hydrophobic microcellulose fiber, it is preferably 50 占 폚 or lower, more preferably 40 占 폚 or lower, and still more preferably 30 占 폚 or lower. The mixing time can be appropriately set according to the type of the amine and the solvent used, but is preferably 0.01 hour or more, more preferably 0.1 hour or more, further preferably 1 hour or more, preferably 48 hours or less Preferably not more than 24 hours, more preferably not more than 12 hours.

After the formation of the salt, a post-treatment may be appropriately performed in order to remove the amine compound not used for salt formation. As the post-treatment method, for example, filtration, centrifugation, dialysis or the like can be used.

As a second method, a method of amidating a microcellulose fiber having a carboxyl group and an amine compound having a silyl group in a solvent can be mentioned.

The amount of the amine compound having the water-soluble group is determined depending on the desired binding amount in the hydrophobic microcellulose fiber. From the viewpoint of reactivity, the amino group is preferably used in an amount of 1 mole of the carboxyl group contained in the carboxyl group-containing microcellulose fiber, More preferably not less than 0.1 mol, more preferably not less than 0.5 mol, still more preferably not less than 0.7 mol, still more preferably not less than 1 mol, from the viewpoint of product purity, preferably not more than 50 mol, more preferably not more than 20 mol, Is used in an amount of 10 mol or less. Amines in the above range may be used either singly or in the form of a reaction.

In the reaction of the carboxyl group-containing microcellulose fiber with an amine compound having a silyl group, a known condensing agent may be used.

Examples of the condensing agent include, but are not limited to, those described in Synthetic Chemistry Series Peptide Synthesis (Maruzen Co.) P116 or a condensation agent described in Tetrahedron, 57, 1551 (2001) Dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (hereinafter sometimes referred to as "DMT-MM").

In the condensation reaction, it is preferable to select a solvent in which the amine compound to be used is dissolved.

The reaction time and the reaction temperature in the condensation reaction can be appropriately selected according to the kind of the amine and the solvent to be used, but are preferably 1 to 24 hours, more preferably 10 to 20 hours from the viewpoint of the reaction rate and the productivity . The reaction temperature is preferably 0 deg. C or more, more preferably 5 deg. C or more, and still more preferably 10 deg. C or more from the viewpoint of reactivity. From the standpoint of coloration of the hydrophobic microcellulose fiber, it is preferably 200 占 폚 or lower, more preferably 80 占 폚 or lower, and still more preferably 30 占 폚 or lower.

After the mixing and after the reaction, post-treatment may be appropriately performed in order to remove unreacted amine compounds and condensing agents. As the post-treatment method, for example, filtration, centrifugation, dialysis or the like can be used.

As a third method, there can be mentioned a method of mixing a microcellulose fiber having a carboxyl group and a quaternary ammonium compound having a water-soluble group in a solvent to prepare a salt.

The amount of the quaternary ammonium compound to be used can be determined according to the desired binding amount in the hydrophobic microcellulose fiber. However, quaternary ammonium cations are preferably used in an amount of 0.1 mol per mol of the carboxyl group contained in the carboxyl group-containing microcellulose fibers, More preferably at least 0.7 mol, even more preferably at least 1 mol, from the viewpoint of product purity, preferably at most 50 mol, more preferably at most 20 mol, even more preferably at most 10 mol Or less. The quaternary ammonium compound in the above range may be used in a salt forming step at one time or may be used in a salt forming step by dividing.

As the solvent, a solvent used when mixing with the amine can be used as well, and water can be used in addition to them. These may be used alone or in combination of two or more. Among them, water, succinic acid and diesters of triethylene glycol monomethyl ether, ethanol and DMF are preferable.

The temperature and time at the time of mixing and the post-treatment after the salt formation can be appropriately set with reference to the case of mixing with the amine compound.

[Curable resin]

The curable resin composition of the present invention is a thermosetting resin composition, a photo-curable resin composition or a photo-curable thermosetting resin composition.

(Thermosetting resin composition)

The thermosetting resin composition of the present invention preferably contains a thermosetting resin, an inorganic filler, and a curing catalyst.

As the thermosetting resin used in the thermosetting resin composition, it is preferable to use a resin having a functional group capable of curing reaction by heat, and a compound having at least one cyclic (thio) ether group in the molecule is preferably used.

Examples of the compound having a cyclic ether group include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol Z type epoxy Novolac epoxy resins such as bisphenol epoxy resins, bisphenol A novolac epoxy resins, phenol novolac epoxy resins and cresol novolac epoxy resins; biphenyl epoxy resins; biphenylaralkyl type epoxy resins; An epoxy resin, an epoxy resin, an arylalkylene type epoxy resin, a tetraphenylol ethane type epoxy resin, a naphthalene type epoxy resin, an anthracene type epoxy resin, a phenoxy type epoxy resin, a dicyclopentadiene type epoxy resin, a norbornene type epoxy resin, Based epoxy resin, a glycidyl methacrylate copolymer-based epoxy resin, a cyclohexyl Polybutadiene rubber derivatives of epoxy-modified, CTBN-modified epoxy resins, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl Hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris (2,3-epoxy Propyl) isocyanurate, and triglycidyl tris (2-hydroxyethyl) isocyanurate; Novolac phenol resins such as phenol novolac resin, cresol novolak resin and bisphenol A novolac resin, unmodified resol phenol resins, oil-modified resol phenol resins modified with tung oil, linseed oil, Phenol resins such as phenol resin; Phenoxy resins; Urea (urea) resin; A triazine ring-containing resin such as melamine resin; A resin having an unsaturated polyester resin, a diallyl phthalate resin, a silicone resin, a resin having a benzoxazine ring, a norbornene resin, a cyanate resin, an isocyanate resin, a urethane resin, a benzocyclobutene resin, a maleimide resin, a bismaleimide triazine resin , Polyazomethine resin, thermosetting polyimide, cyanate ester resin, and active ester resin.

As the thermosetting resin, it is preferable to include an epoxy resin and a phenol resin. By including an epoxy resin and a phenol resin, heat resistance, peel strength, insulation reliability, and the like can be improved. The content of the epoxy resin is, for example, not less than 1 part by mass and not more than 90 parts by mass, preferably not less than 10 parts by mass and not more than 85 parts by mass, more preferably not less than 20 parts by mass and not less than 80 parts by mass based on 100 parts by mass of the entire thermosetting resin Or less. The content of the phenol resin is, for example, 1 part by mass or more and 70 parts by mass or less, preferably 5 parts by mass or more and 60 parts by mass or less, and more preferably 10 parts by mass or more and 50 parts by mass or less, based on the entire thermosetting resin.

When an active ester resin is used as the thermosetting resin, the use of dimethylaminopyridine improves the curability.

In the curable resin composition of the present invention, by using the microcellulose fiber and the inorganic filler in combination, the effect of reducing the linear expansion coefficient of the cured product is excellent.

Examples of the inorganic 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 and aluminum nitride. Among these inorganic fillers, silica is preferred because it has a small specific gravity, is capable of being blended in a high proportion in the composition, and is excellent in low-temperature expandability.

In the curable resin composition of the present invention, a combination of microcellulose fiber and silica is suitable. In this case, the effect of reducing the linear expansion coefficient of the cured product is more excellent, and the adhesion with the metal conductor is further improved.

The average particle diameter of the inorganic filler is preferably 3 mu m or less, more preferably 1 mu m or less. The average particle diameter of the inorganic filler can be obtained by a laser diffraction particle diameter distribution measuring apparatus.

The blending amount of the inorganic filler is, for example, 25 to 90 mass%, preferably 30 to 90 mass%, and more preferably 35 to 85 mass% with respect to the solid content of the composition. When the blending amount of the inorganic filler is within the above range, the coating performance of the cured product after curing can be satisfactorily secured.

The curing catalyst is for curing a thermosetting resin mainly in the curable resin and includes, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl- Imidazole derivatives such as phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) ; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; Phosphorus compounds such as triphenylphosphine, and dimethylaminopyridine. U-CAT3503N, U-CAT3502T, DBU, DBN, U-CATSA102, U-CATSA102, and U-CATSA102 are commercially available products such as 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (manufactured by Shikoku Chemicals Corporation) And CAT5002 (manufactured by SANA PRO) can be used alone or in combination of two or more kinds. Likewise, it is also possible to use, for example, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2- Triazine, isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, isocyanuric acid, S-triazine derivatives such as acid adducts may also be used.

As the curing catalyst, a basic catalyst is preferred. In particular, imidazoles are preferred, and by using imidazoles, both the curability and stability of the composition can be achieved, and the heat resistance can be improved. The content of the curing catalyst is, for example, from 0.01 to 20 parts by mass, preferably from 0.05 to 15 parts by mass, and more preferably from 0.1 to 15 parts by mass relative to 100 parts by mass of the thermosetting resin .

In addition to hydrophobic microcellulose fibers, thermosetting resins, inorganic fillers, and curing catalysts, the thermosetting resin composition of the present invention can be blended with other blending components for general use according to the use thereof.

Examples of other compounding ingredients for tolerance include colorants, organic solvents, dispersants, defoamers and leveling agents, thixotropic agents, coupling agents, flame retardants and the like.

As the coloring agent, a coloring pigment, a dye, or the like known in color index can be used. For example, Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, Solvent Blue 35, 63, 68, 70, 83, 87, 122, 136, 67, 70, Pigment Green 7, 36, 3, 5, 20, 28, Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, 110, 109, 139, 179, 185, 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, 12, 13, 14, 16, 17, 55, 63, Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, Pigment Red 1, 2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32, 48, 2, 3, 4, 5, 6, 26, 26, 26, 37, 38, 41, 48, 52: 1, 52: 2, 53: 1, 53: 2, 57: 1, 58: 4, 63: 1, 63: 1, 48: 3, 48: 4, 49: 2, 64: 1, 68, 171, 175, 176, 185, 208, 123, 149, 166, 178, 179, 190, 194, 224, 254, 255, 264, 270, 272, 220, 214, 22 Solvent Red 135, 179, 149, 150, 52, 207, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, Pigment Brown 23, 25, Pigment Black 1, 7, and the like.

The content of the colorant is, for example, 0.01 mass% or more and 3 mass% or less, preferably 0.05 mass% or more and 1 mass% or less, and more preferably 0.1 mass% or more and 0.5 mass% or less, When a white cured film is obtained by using titanium oxide or the like, the total composition contains, for example, 1 mass% or more and 65 mass% or less, preferably 3 mass% or more and 60 mass% or less, more preferably 5 mass% Or more and 50 mass% or less.

Examples of the organic solvent include 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. Of glycol ethers; Esters such as ethyl acetate, butyl acetate, cellosolve acetate, diethylene glycol monoethyl ether acetate and esters of the glycol ethers; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Amides such as dimethylformamide and dimethylacetamide; aliphatic hydrocarbons such as octane and decane; Petroleum ether such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha.

Examples of the dispersing agent include polymer dispersing agents such as polycarboxylic acid type, naphthalenesulfonic acid formalin condensation type, polyethylene glycol, polycarboxylic acid partial alkyl ester type, polyether type, and polyalkylene polyamine type, alkylsulfonic acid type, quaternary ammonium type, And low-molecular dispersants such as higher alcohol alkylene oxide-based, polyhydric alcohol ester-based, alkylpolyamine-based, and the like.

Examples of the antifoaming agents and leveling agents include silicones, modified silicones, mineral oils, vegetable oils, aliphatic alcohols, fatty acids, metal soaps, fatty acid amides, polyoxyalkylene glycols, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, Can be used.

As a thixotropic agent, particulate silica, silica gel, amorphous inorganic particles, polyamide-based additives, modified urea-based additives, wax-based additives and the like can be used.

Examples of the coupling agent include a methoxy group, an ethoxy group and an acetyl group as the alkoxy group, and examples of the reactive functional group include vinyl, methacryl, acrylic, epoxy, cyclic epoxy, mercapto, amino, diamino, acid anhydride, , Vinyl-based silane compounds such as vinyl ethoxysilane, vinyltrimethoxysilane, vinyl tris (? -Methoxyethoxy) silane and? -Methacryloxypropyltrimethoxysilane,? -Aminopropyl (Aminoethyl)? - aminopropylmethyldimethoxysilane,? - ureidopropyltriethoxysilane, and the like can be used as the silane coupling agent, such as trimethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, Epoxy silane compounds such as amino silane compounds,? - glycidoxypropyltrimethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane and? -Glycidoxypropylmethyldiethoxysilane, such as? -mercaptopropyltrimethoxysilane Silane coupling agents such as mercapto silane compounds and phenylamino silane compounds such as N-phenyl-gamma -aminopropyltrimethoxysilane, isopropyl triisostearoyl titanate, tetraoctyl bis (ditridecyl phosphite) (Dioctyl pyrophosphate) oxyacetate titanate, isopropyltridodecylbenzene sulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctylphosphite) (Ditridecylphosphate) ethylene titanate, isopropyltri octanoyl titanate, isopropyl tin octanoate titanate, tetra (1,1-diallyloxymethyl-1-butyl) Isopropyltrimethacrylate, isopropyltrimethacrylate, isopropyldimethacrylate, isostearyl acrylate, isopropyldimethacrylate, isostearyl acrylate, isopropyltrimethacrylate, isopropyltrimethacrylate, Titanate-based coupling agents such as phenyltrimethylammonium phenyl titanate, dicumylphenyloxyacetate titanate and diisostearoylethylenetitanate, ethylenically unsaturated zirconate-containing compounds, neoalkoxyzirconate-containing compounds, neoalkoxy (Dioctyl) phosphate zirconate, neoalkoxytris (dioctyl) pyrophosphate zirconate, neoalkoxytris (dodecyl) benzenesulfonylate, neoalkoxytris (Ethylene diamino) ethyl zirconate, neoalkoxytris (m-amino) phenyl zirconate, tetra (2,2-diallyloxymethyl) butyl, di (ditridecyl) phosphite zirconate, neopentyl (Diallyl) oxy, trienodecanoyl zirconate, neopentyl (diallyl) oxy, tri (dodecyl) benzene-sulfonyl zirconate, neopentyl (diallyl) Tri (dioctyl) phosphatozirconate, neopentyl (diallyl) oxy, tri (N-ethylenediamino) ethylglycine, (Diallyl) oxy, tri (m-amino) phenyl zirconate, neopentyl (diallyl) oxy, trimethacrylic zirconate, neopentyl (diallyl) oxy, triacrylic zirconate , Dienopentyl (diallyl) oxy, diparaaminobenzoyl zirconate, dineopentyl (diallyl) oxy, di (3-mercapto) propionic zirconate, zirconium (IV) Zirconate coupling agents such as cyclopyrrolopyrrole, 2-propenolatomethyl) butanolato, cyclodi [2,2- (bis 2-propanolatomethyl) butanolato] pyrophosphato-O and O, diisobutyl An aluminate-based coupling agent such as acetoacetyl aluminate and alkyl acetoacetate aluminum diisopropylate may be used have.

Examples of the flame retardant include metal hydroxides such as aluminum hydroxide and magnesium hydroxide, ammonia, ammonium phosphate, ammonium carbonate, zinc borate, zinc stannate, molybdenum compound, bromine compound, chlorine compound, phosphoric acid ester, phosphorus- Melamine cyanurate, melamine compound, triazine compound, guanidine compound, silicone polymer and the like can be used.

(Photo-curable resin composition)

The photocurable resin composition of the present invention preferably contains a photocurable resin, an inorganic filler, a photopolymerization initiator, and a colorant.

As the photo-curable resin, it is preferable to use a resin having a functional group capable of curing reaction by irradiation with active energy rays, and it may be radical polymerizable or cationic polymerizable.

For example, a compound having at least one ethylenic unsaturated bond in the molecule, an alicyclic epoxy compound, and an oxetane compound, and a compound having at least one ethylenic unsaturated bond in the molecule are preferably used.

As the compound having an ethylenically unsaturated bond, a photopolymerizable oligomer and a photopolymerizable vinyl monomer for publicly known generations are used.

Examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers. (Meth) acrylate oligomers include epoxy (meth) acrylates such as phenol novolak epoxy (meth) acrylate, cresol novolak epoxy (meth) acrylate, and bisphenol epoxy (meth) Acrylate, epoxy urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate and polybutadiene modified (meth) acrylate.

In the present specification, the term (meth) acrylate is generically referred to as acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

Examples of the photopolymerizable vinyl monomer include known ones such as styrene derivatives such as styrene, chlorostyrene, and? -Methylstyrene; Vinyl esters such as vinyl acetate, vinyl butyrate and vinyl benzoate; N-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether Vinyl ethers such as ether and triethylene glycol monomethyl vinyl ether; Acrylamides such as acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide and N-butoxymethylacrylamide Meta) acrylamides; Allyl compounds such as triallyl isocyanurate, diallyl phthalate and diallyl isophthalate; (Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl Esters of (meth) acrylic acid such as acrylate; Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and pentaerythritol tri (meth) acrylate; Alkoxyalkylene glycol mono (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; Acrylates such as ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6- hexanediol di (meth) acrylate, trimethylolpropane tri (Meth) acrylates such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Polyoxyalkylene glycol poly (meth) acrylates such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri Methacrylate; Poly (meth) acrylates such as hydroxypivalic acid neopentyl glycol ester di (meth) acrylate; And isocyanurate type poly (meth) acrylates such as tris [(meth) acryloxyethyl] isocyanurate.

Examples of the alicyclic epoxy compound include 3,4,3 ', 4'-diepoxybicyclohexyl, 2,2-bis (3,4-epoxycyclohexyl) propane, 2,2-bis (3,4-epoxycyclohexyl (3,4-epoxycyclohexyl) methane, 1- [1,1-bis (3,4-epoxycyclohexyl)] ethylbenzene, bis Epoxycyclohexyl) adipate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, (3,4-epoxy-6-methylcyclohexyl) methyl-3 ', 4'- (3,4-epoxycyclohexanecarboxylic acid) ester, cyclohexene oxide, 3,4-epoxycyclohexylmethyl alcohol, 3,4-epoxycyclohexanecarboxylic acid, And alicyclic epoxy compounds having an epoxy group such as cyclohexylethyltrimethoxysilane.

As a commercial product, for example, Celllock 2000, Celloxide 2021, Celllock 3000, EHPE 3150, manufactured by Daicel Chemical Industries, Ltd.; Epomic VG-3101 manufactured by Mitsui Chemicals, Inc.; E-1031S manufactured by Yucca Shell Epoxy; TETRAD-X and TETRAD-C of Mitsubishi Gas Chemical Company; EPB-13 and EPB-27 manufactured by Nippon Soda Co., Ltd., and the like.

Examples of the oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [ Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-ethyl-3-oxetanyl) methyl methacrylate, (3-methyl-3-oxetanyl) methyl methacrylate, Or polyfunctional oxetanes such as polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene, An oxetane compound such as a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate, and the like.

OXT-211, OXT-221, OXT-212, and OXT-212 manufactured by Ube Kosan Co., Ltd., , OXT-610, and PNOX-1009.

The photopolymerization initiator is for curing the photopolymerizable resin in the curable resin, and may be a photo radical polymerization initiator or a photo cationic polymerization initiator.

Examples of the photo radical polymerization initiator include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc. Acetophenones; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- Aminoalkylphenones such as 1,2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone; Anthraquinones such as 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, and 1-chloro anthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone; Or xanthones; (2,6-dimethoxybenzoyl) -2,4,4-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine Phosphine oxides such as oxide and ethyl 2,4,6-trimethylbenzoyl phenylphosphinate; Various peroxides, titanocene initiators, and the like. These include photoinitiators such as tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine and triethanolamine Or may be used in combination.

Examples of the photo cationic polymerization initiator include onium salts such as diazonium salts, iodonium salts, bromonium salts, chloronium salts, sulfonium salts, selenonium salts, pyrylium salts, thiapyrylium salts and pyridinium salts; Halogenated compounds such as tris (trihalomethyl) -s-triazine and its derivatives; 2-nitrobenzyl ester of sulfonic acid; Iminosulfonate; 1-oxo-2-diazonaphthoquinone-4-sulfonate derivatives; N-hydroxyimide = sulfonate; Tri (methanesulfonyloxy) benzene derivatives; Bis-sulfonyldiazomethanes; Sulfonylcarbonylalkanes; Sulfonylcarbonyldiazomethanes; Disulfone compounds and the like.

These photopolymerization initiators may be used alone or in combination of two or more.

The blending amount of the photopolymerization initiator is, for example, 0.05 to 20 parts by mass, preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the photocurable resin in terms of solid content. By incorporating the photopolymerization initiator in this range, the photocurability on copper becomes satisfactory, the curability of the coating film becomes good, the coating film characteristics such as chemical resistance are improved, and the deep portion curability is also improved.

As the inorganic filler, those similar to those used in the above-mentioned thermosetting resin composition can be used, and the blending amount can also be used.

As the colorant, those similar to those used in the thermosetting resin composition can be used. By including the colorant, deterioration of the adhesiveness can be prevented even when an excessive amount of accumulated light is irradiated in the photo-curable resin composition. Further, the visibility of the coating film can be improved.

In addition to the hydrophobic microcellulose fiber, the photo-curing resin, the inorganic filler, the photopolymerization initiator and the coloring agent, the photocurable resin composition of the present invention can appropriately blend other blending ingredients for general use according to the use thereof.

Examples of other compounding ingredients for tolerance include organic solvents, dispersants, defoamers and leveling agents, thixotropic agents, coupling agents, flame retardants and the like. As the organic solvent, dispersant, defoaming agent, leveling agent, thixotropic agent, coupling agent, and flame retardant, the same thermosetting resin composition as the composition can be used.

(Photo-curable thermosetting resin composition)

The photo-curable thermosetting resin composition of the present invention comprises a photo-curable resin and a thermosetting resin. When the photo-curable thermosetting resin composition of the present invention is a development type using an aqueous alkali solution, .

The carboxyl group-containing resin can be a photosensitive carboxyl group-containing resin having at least one photosensitive unsaturated double bond and a carboxyl group-containing resin having no photosensitive unsaturated double bond, and is not limited to a specific one. In particular, the resins listed below can be suitably used.

(1) a carboxyl group-containing resin obtained by copolymerization of a compound having an unsaturated carboxylic acid and an unsaturated double bond, and a carboxyl group-containing resin obtained by modifying the molecular weight and acid value thereof.

(2) A carboxyl group-containing photosensitive resin obtained by reacting a carboxyl group-containing (meth) acrylic copolymer resin with a compound having an oxirane ring and an ethylenically unsaturated group in one molecule.

(3) an unsaturated monocarboxylic acid is reacted with a copolymer of a compound having an epoxy group and an unsaturated double bond in each molecule and a compound having an unsaturated double bond, and the unsaturated monocarboxylic acid is saturated with a second-class hydroxyl group generated by the reaction Or an unsaturated polybasic acid anhydride.

(4) a method of reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, and then reacting the resulting carboxylic acid with a compound having one epoxy group and one unsaturated double bond in one molecule, Photosensitive resin.

(5) A carboxyl group-containing photosensitive resin obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid, and reacting a part or all of the polybasic acid anhydride with the second-class hydroxyl group generated by the reaction.

(6) A process for producing a polyfunctional epoxy compound, which comprises reacting a polyfunctional epoxy compound and a compound having at least two reactive groups other than a hydroxyl group reacting with at least two hydroxyl groups and an epoxy group in a molecule with a monocarboxylic acid containing an unsaturated group, A carboxyl group-containing photosensitive resin.

(7) A carboxyl group-containing photosensitive resin obtained by reacting a reaction product of a resin having a phenolic hydroxyl group with an alkylene oxide with a monocarboxylic acid containing an unsaturated group, and reacting the obtained reaction product with a polybasic acid anhydride.

(8) A process for producing a polyfunctional epoxy compound, which comprises reacting a polyfunctional epoxy compound, a compound having at least one alcoholic hydroxyl group and at least one phenolic hydroxyl group in a molecule with an unsaturated group-containing monocarboxylic acid, A carboxyl group-containing photosensitive resin obtained by reacting an anhydride group.

As the photo-curing resin and the thermosetting resin used in the photo-curable thermosetting resin composition of the present invention, the same photo-curable resin and thermosetting resin as those described above can be used. The photocurable thermosetting resin composition of the present invention preferably contains the inorganic filler, the curing catalyst and the photopolymerization initiator described above, and it is possible to appropriately blend other blending components for general use according to the use thereof.

Examples of other compounding ingredients for tolerance include the above-mentioned coloring agents, organic solvents, dispersants, defoamers and leveling agents, thixotropic agents, coupling agents, flame retardants and the like.

The curable resin composition of the present invention may be used as a dry film or as a liquid phase. When used as a liquid phase, it may be one-liquid or two-liquid or more. The two-component composition may be, for example, a composition obtained by dividing hydrophobic microcellulose fibers and a curable resin.

Next, the dry film of the present invention has a resin layer obtained by applying and drying the curable resin composition of the present invention on a carrier film. When the dry film is formed, first, the curable resin composition of the present invention is diluted with the organic solvent and adjusted to an appropriate viscosity. Thereafter, a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, , A gravure coater, a spray coater, or the like, on the carrier film in a uniform thickness. Thereafter, the applied composition is dried at a temperature of usually 40 to 130 DEG C for 1 to 30 minutes to form a resin layer. The thickness of the coating film is not particularly limited, but is generally appropriately selected in the range of 3 to 150 占 퐉, preferably 5 to 60 占 퐉 in the film thickness after drying.

As the carrier film, a plastic film is used. For example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film and the like can be used. The thickness of the carrier film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 mu m. More preferably in the range of 15 to 130 mu m.

A peelable cover film is further laminated on the surface of the resin layer for the purpose of preventing the attachment of dust to the surface of the resin layer after the resin layer containing the curable resin composition of the present invention is formed on the carrier film . As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper and the like can be used. As the cover film, the adhesive force between the cover film and the resin layer when peeling the cover film is smaller than the adhesive force between the resin layer and the carrier film.

In the present invention, a resin layer may be formed by applying and drying the curable resin composition of the present invention on the cover film, and a carrier film may be laminated on the surface of the resin layer. That is, in the present invention, as a film to which the curable resin composition of the present invention is applied when producing a dry film, either a carrier film or a cover film may be used.

The printed wiring board of the present invention has a cured product obtained from the resin layer of the curable resin composition or the dry film of the present invention. As a method for producing the printed wiring board of the present invention, first, for example, the curable resin composition of the present invention is adjusted to a viscosity suitable for the application method by using the above-mentioned organic solvent and dip coating, flow coating, (By drying) the organic solvent contained in the composition at a temperature of 60 to 100 ° C after coating by a coating method, a bar coater method, a screen printing method, a curtain coating method or the like, . Further, in the case of a dry film, the resin layer is bonded to a substrate such that the resin layer comes into contact with the substrate by a laminator or the like, and then the carrier film is peeled off to form a resin layer on the substrate.

Examples of the substrate include a substrate such as a paper phenol, a paper epoxy, a glass cloth epoxy, a glass polyimide, a glass cloth / nonwoven epoxy, a glass cloth / paper epoxy, a synthetic fiber epoxy, a fluororesin · Copper-clad laminate for high-frequency circuit using polyethylene · Polyphenylene ether, polyphenylene oxide · cyanate, etc., and it is possible to use copper clad laminate of all grades (FR-4 etc.), metal substrate, polyimide film , A PET film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, and a wafer plate.

The volatile drying after application of the curable resin composition of the present invention can be carried out by a hot-air circulating drying furnace, a hot plate, a convection oven or the like (which is equipped with a heat source of air heating by steam) A method of bringing the nozzle into contact with the support, and a method of spraying the solution from the nozzle onto the support).

When the composition of the present invention is a thermosetting resin composition, a composition is applied to a substrate to form a coating film, or a dry film is laminated to form a resin layer, followed by heating to a temperature of, for example, about 100 to 180 ° C (Cured product) having various properties such as heat resistance, chemical resistance, hygroscopicity, adhesion, electrical properties and the like can be formed by heat curing.

When the composition of the present invention is a photo-curable resin composition, a composition is applied to a substrate to form a coating film, or a dry film is laminated to form a resin layer, and then an active energy ray is irradiated to form a cured film (cured product) . If necessary, the coating film may be heated before irradiation with an active energy ray.

When the composition of the present invention is an alkali developing type photocurable thermosetting resin composition, after a resin layer is formed on a printed wiring board, the resin layer is selectively exposed through an active energy ray through a photomask having a predetermined pattern, The light portion is developed with a dilute aqueous alkali solution (for example, 0.3 to 3 mass% aqueous solution of sodium carbonate) to form a pattern of the cured product. Further, by irradiating the cured product with an active energy ray and then curing by heating (for example, 100 to 220 ° C), or by irradiating an active energy ray after heat curing, or by final curing (final curing) , Hardness, and the like. Further, the composition of the present invention may be an unexplained photocurable thermosetting resin composition containing the above-mentioned thermosetting resin and a photocurable resin and not subjected to development processing.

As an exposure device used for the irradiation of the active energy ray, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like may be used, and an apparatus for irradiating ultraviolet rays in a range of 350 to 450 nm may be used. (E. G., A laser direct imaging device that draws images directly with a laser by CAD data from a computer). As the lamp light source or the laser light source of the direct game machine, the maximum wavelength may be in the range of 350 to 450 nm. Light exposure for image formation film varies, depending upon the thickness, but in general can be within the 10 to 1000mJ / cm ^2, preferably in the range of 20 to a range of 800mJ / cm ^2.

Examples of the developing method include a dipping method, a shower method, a spraying method, a brushing method and the like. As the developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, .

Example

Hereinafter, the present invention will be described in more detail with reference to examples. In the following table, the amounts are all parts by mass.

[Preparation of oxidized pulp]

(Oxidized pulp 1)

Bleached kraft pulp of conifer (Fletcher Challenge Canada, trade name " Machenzie ", CSF 650 ml) was used as the natural cellulose fiber. As the TEMPO, a commercially available product (ALDRICH, Free radical, 98% by mass) was used. As sodium hypochlorite, a commercially available product (manufactured by Wako Pure Chemical Industries, Ltd.) was used. As sodium bromide, a commercially available product (manufactured by Wako Pure Chemical Industries, Ltd.) was used.

First, 100 g of the bleached kraft pulp fiber of conifer was sufficiently stirred with 9900 g of ion-exchanged water, and then 1.25 mass% of TEMPO, 12.5 mass% of sodium bromide and 28.4 mass% of sodium hypochlorite were added in this order to 100 g of this pulp mass . Using a pH-stud, 0.5 M sodium hydroxide was added dropwise to maintain the pH at 10.5. After the reaction was carried out for 120 minutes (20 占 폚), the dropwise addition of sodium hydroxide was stopped to obtain oxidized pulp. The oxidized pulp obtained by using ion-exchanged water was thoroughly washed, and then subjected to dehydration treatment to obtain oxidized pulp having a solid content of 30.4%.

(Oxidized pulp 2)

Oxidized pulp having a solid content of 30.4% was obtained in the same manner as in the case of the oxidized pulp 1 except that the raw material used was changed to a hardwood bleached craft pulp derived from eucalyptus (manufactured by CENIBRA).

[Preparation of microcellulose fiber aqueous dispersion]

(Production Example 1)

1.18 g of oxidized pulp 1 and 34.8 g of ion-exchanged water were subjected to fineness treatment at 150 MPa for 10 times using a high-pressure homogenizer to obtain a carboxyl-group-containing microcellulose fiber dispersion (solid concentration 5.0 mass%). The average fiber diameter of the microcellulose fibers was 2.7 nm, the average fiber length was 578 nm, the average aspect ratio was 214, and the carboxyl group content was 1.4 mmol / g.

(Production Example 2)

105.3 g of the oxidized pulp 1 was diluted with 1000 g of ion-exchanged water and 346 g of concentrated hydrochloric acid was added to prepare a dispersion having a concentration of solidified pulp of 2.34% by weight and a hydrochloric acid concentration of 2.5 M and refluxed for 3 minutes. The obtained oxidized pulp was thoroughly washed to obtain an acid hydrolyzed TEMPO oxidized pulp having a solid content of 41%. Thereafter, 0.88 g of oxidized pulp and 35.12 g of ion-exchanged water were subjected to refinement treatment at 150 MPa for 10 times using a high-pressure homogenizer to obtain a carboxyl group-containing microcellulose fiber dispersion (solid concentration: 5.0% by mass). The average fiber diameter of the microcellulose fibers was 2.9 nm, the average fiber length was 491 nm, the average aspect ratio was 169, and the carboxyl group content was 1.4 mmol / g.

(Production Example 3)

The carboxyl group-containing microcellulose fiber was prepared in the same manner as in Preparation Example 2 except that the refluxing time was changed to 10 minutes. The microfine cellulose fibers had an average fiber diameter of 4.6 nm, an average fiber length of 331 nm, an average aspect ratio of 72, a carboxyl group content of 1.4 mmol / g and a solid content concentration of 5.0% by mass of the carboxyl group-containing microcellulose fiber dispersion.

(Production Example 4)

Carboxyl group-containing microcellulose fibers were produced in the same manner as in Production Example 3 except that oxidized pulp 2 was used. The average microfine cellulose fibers had an average fiber diameter of 11.0 nm, an average fiber length of 187 nm, an average aspect ratio of 17, a carboxyl group content of 1.1 mmol / g, and a solid content concentration of 5.0% by mass of the carboxyl group-containing microcellulose fiber dispersion.

(Production Example 5)

Carboxyl group-containing microcellulose fiber was prepared in the same manner as in Production Example 4, except that the refluxing time was changed to 60 minutes. The microcellulose fibers had an average fiber diameter of 19.4 nm, an average fiber length of 174 nm, an average aspect ratio of 9, a carboxyl group content of 1.1 mmol / g and a solid content concentration of 5.0% by mass of the carboxyl group-containing microcellulose fiber dispersion.

[Preparation of dispersion of microcellulose fiber DMF having a receiver]

(CNF1)

40 g (solid concentration: 5.0% by mass) of the microcellulose fibers obtained in Preparation Example 1 was added to a beaker equipped with a magnetic stirrer and a stirrer. Subsequently, aniline was added to 0.34 g of 4-methylmorpholine and 1.98 g of DMT-MM as a condensing agent in an amount corresponding to 1.2 mol of the amino group to 1 mol of the carboxyl group of the microcellulose fiber and dissolved in 300 g of DMF. The reaction solution was reacted at room temperature (25 ° C) for 14 hours. After completion of the reaction, the reaction mixture was filtered, washed with ethanol, and the DMT-MM salt was removed. The DMF-MM salt was washed with DMF and replaced with a solvent to obtain a DMF dispersion of microcellulose fibers in which aromatic hydrocarbon groups were bonded via amide bonds to the microcellulose fibers. The solid content concentration of the resulting microcellulose fiber DMF dispersion was 2.2% by mass.

(CNF2)

A microcellulose fiber DMF dispersion (solid content: 5.0% by mass) was obtained in the same manner as in CNF1 except that the microcellulose fibers obtained in Preparation Example 1 were replaced with the microcellulose fibers obtained in Preparation Example 2 as the microcellulose fibers.

(CNF3)

35 g (solid content concentration: 5 mass%) of the fine cellulose fiber obtained in Production Example 2 was added to a beaker equipped with a stirrer and a magnetic stirrer. Subsequently, tetrabutylammonium hydroxide was added in an amount corresponding to 1 mol of the amino group to 1 mol of the carboxyl group of the microcellulose fiber, and dissolved in 300 g of DMF. The reaction solution was reacted at room temperature (25 ° C) for 1 hour. After completion of the reaction, the reaction product was filtered and washed with DMF to obtain microcellulose fibers having an amine salt bonded to the microcellulose fibers. The solid content concentration of the resulting microcellulose fiber DMF dispersion was 4.0% by mass.

(CNF4)

Except that the microcellulose fibers obtained in Preparation Example 2 were replaced with the fine cellulosic fibers obtained in Preparation Example 3 and the tetrabutylammonium hydroxide was replaced with JEFFAMINE M-600 (manufactured by HUNTSMAN) as the fine cellulosic fibers, A cellulose fiber DMF dispersion (solid content 8.0% by mass) was obtained.

(CNF5)

A microcellulose fiber DMF dispersion (solid content 12.0 mass%) was obtained in the same manner as CNF1 except that the microcellulose fibers obtained in Preparation Example 1 were changed to the microcellulose fibers obtained in Preparation Example 4 as microcellulose fibers.

(CNF6)

A microcellulose fiber DMF dispersion (solid content 13.0% by mass) was obtained in the same manner as in CNF1 except that the microcellulose fibers obtained in Preparation Example 1 were replaced with the microcellulose fibers obtained in Preparation Example 5 and the aniline was changed to octadecylamine. ≪ / RTI >

These microcellulose fibers are collectively shown in Table 1 below.

[Production of carboxyl group-containing resin for use in curable resin composition]

[Synthesis Example 1]

(Varnish 1)

A 2-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate (Trade name: Perbutyl O, manufactured by Nippon Steel Chemical Co., Ltd.), and the mixture was heated to 90 占 폚. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (Daicel Co., Ltd., trade name: Flaccel FM1) (4-t-butylcyclohexyl) peroxydicarbonate (manufactured by Nichiyu Corporation, product name: Perillo TCP) was added dropwise over 3 hours. This was aged for 6 hours to obtain a carboxyl group-containing copolymer resin. These reactions were carried out in a nitrogen atmosphere.

Then, 363.9 g of 3,4-epoxycyclohexylmethylacrylate (Daicel Co., Ltd., product name: Cychroma A200), 3.6 g of dimethylbenzylamine as a ring-opening catalyst, 5 g of hydroquinone monomethyl 1.80 g of ether was added and the mixture was heated to 100 占 폚 and stirred to carry out the ring-opening addition reaction of epoxy. After 16 hours, a solution containing 53.8% by mass (nonvolatile content) of a carboxyl group-containing resin having an acid value of solid content of 108.9 mgKOH / g and a mass average molecular weight of 25,000 was obtained.

[Synthesis Example 2]

(Varnish 2)

Diethylene glycol monoethyl ether acetate as a solvent and azobisisobutyronitrile as a catalyst were placed in a flask equipped with a stirrer, a thermometer, a stirrer, a dropping funnel and a reflux condenser, and the mixture was heated to 80 DEG C under a nitrogen atmosphere, The monomer mixture of methyl methacrylate at a molar ratio of 0.40: 0.60 was added dropwise over about 2 hours. After stirring for 1 hour, the temperature was raised to 115 캜, and the solution was deactivated to obtain a resin solution.

After the resin solution was cooled, butylglycidyl ether was added thereto at a molar ratio of 0.40 under the condition of 95 to 105 ° C for 30 hours using tetrabutylammonium bromide as a catalyst, and the resultant was subjected to addition reaction with the carboxyl group equivalent of the obtained resin , And cooled.

Further, the OH group of the resin obtained above was subjected to an addition reaction at a molar ratio of 0.26 of anhydrous tetrahydrophthalic acid under the condition of 95 to 105 캜 for 8 hours. This was taken out after cooling to obtain a solution containing 50 mass% (nonvolatile content) of a carboxyl group-containing resin having an acid value of a solid content of 78.1 mgKOH / g and a mass average molecular weight of 35,000.

[Synthesis Example 3]

(Varnish 3)

210 g of cresol novolak type epoxy resin (Epiclon N-680, manufactured by DIC Corporation, epoxy equivalent = 210) and 96.4 g of carbitol acetate as a solvent were placed in a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser Followed by heating and dissolution. Then, 0.1 g of hydroquinone as a polymerization inhibitor and 2.0 g of triphenylphosphine as a reaction catalyst were added thereto. The mixture was heated to 95 to 105 DEG C, and 72 g of acrylic acid was gradually added dropwise, and the reaction was carried out for about 16 hours until the acid value became 3.0 mgKOH / g or less. After the reaction product was cooled to 80 to 90 캜, 76.1 g of tetrahydrophthalic anhydride was added and reacted for about 6 hours by infrared absorption analysis until the absorption peak (1780 cm ^-1 ) of the acid anhydride disappeared. To this reaction solution, 96.4 g of aromatic solvent Solp Sol # 150 manufactured by Idemitsu Kosan Co., Ltd. was added, and the solution was taken out after dilution. The thus-obtained photosensitive polymer solution containing the carboxyl group had a nonvolatile content of 65% by mass and an acid value of a solid content of 78 mgKOH / g.

[Preparation of curable resin composition]

Each component was mixed and stirred in accordance with the description in the following Tables 2 to 6, and then each composition was prepared by dispersing it six times using a high-pressure homogenizer Nanovater NVL-ES008 manufactured by Yoshida Kagai Kogyo Co., Ltd. The numerical values in Tables 2 to 6 indicate mass parts.

<Viscosity Measurement>

The viscosity of each composition was measured using a cone plate 1 ° 34 'with an axon contact cone plate type viscometer TPE-100-H at a rotation number of 0.5 rpm. The results are shown in Tables 2 to 6. In addition, it was impossible to make a composition that could not be measured beyond the measurement limit of the apparatus.

&Lt; Preparation of sample for thermal expansion measurement >

(Thermosetting resin composition)

Each composition was coated on a PET film having a thickness of 38 mu m with an applicator having a gap of 120 mu m and dried at 90 DEG C for 10 minutes in a hot air circulation type drying furnace to obtain a dry film having a resin layer of each composition. Then, a copper foil having a thickness of 18 탆 was pressed in a vacuum laminator at 60 캜 under a pressure of 0.5 MPa for 60 seconds to laminate the resin layers of each composition, and the PET film was peeled off. Then, it was cured by heating in a hot air circulation type drying furnace at 180 DEG C for 30 minutes, and the copper foil was peeled off to obtain a sample of the cured film. Further, it was considered impossible to prepare a composition which had a high viscosity and could not be applied with an applicator.

(Photo-curable resin composition)

A copper foil having a thickness of 18 mu m was attached to an FR-4 copper clad laminate having a thickness of 1.6 mm, each composition was coated with an applicator having a gap of 120 mu m, and dried in a hot air circulation type drying oven at 90 DEG C for 10 minutes. Thereafter, the sample was irradiated with a cumulative light quantity of 2000 mJ / cm ² using a conveyor type high-pressure mercury lamp of 120 W / cm. Then, the copper foil was peeled off to obtain a sample of the cured film. Further, it was considered impossible to prepare a composition which had a high viscosity and could not be applied with an applicator.

(Photo-curable thermosetting resin composition)

A copper foil having a thickness of 18 mu m was attached to an FR-4 copper clad laminate having a thickness of 1.6 mm, each composition was coated with an applicator having a gap of 120 mu m, and dried in a hot air circulation type drying oven at 90 DEG C for 10 minutes. Thereafter, a negative mask with a pattern of 3 mm wide × 30 mm long was closely contacted and exposed at 700 mJ / cm ² using a metal halide lamp exposure apparatus for printed wiring boards. Subsequently, the resist film was developed with a developer of 1 wt% Na ₂ CO ₃ at 30 ° C for 60 seconds. Thereafter, it was cured by heating in a hot air circulation type drying furnace at 150 DEG C for 60 minutes, and the copper foil was peeled off to obtain a sample of the cured film. Further, it was considered impossible to prepare a composition which had a high viscosity and could not be applied with an applicator.

<Measurement of Thermal Expansion Rate>

(Thermosetting resin composition and photocurable resin composition)

The prepared thermal expansion measurement sample was cut into a length of 3 mm width x 30 mm. This test piece was heated in a tensile mode at a rate of 5 DEG C / min from 20 to 250 DEG C under a nitrogen atmosphere at a chuck distance of 16 mm and a load of 30 mN using TMA (Thermomechanical Analysis) Q400 manufactured by T.A. And then cooled at a rate of 5 DEG C / min. An average coefficient of thermal expansion? 1 at 30 DEG C to 100 DEG C during the temperature lowering and an average coefficient of thermal expansion? 2 at 200 DEG C to 230 DEG C were obtained. The results are shown in Tables 2 to 6.

(Photo-curable thermosetting resin composition)

The same procedure as in the case of the thermosetting resin composition and the photo-curing resin composition was carried out except that the prepared sample was used as it was. The results are shown in Tables 2 to 6.

&Lt; Preparation of sample for measuring the peel strength of plated copper &

(Thermosetting resin composition)

Each composition was applied to a PET film having a thickness of 38 mu m with an applicator having a gap of 120 mu m and dried at 90 DEG C for 10 minutes in a hot air circulation type drying furnace to obtain a dry film having a resin layer of each composition. Thereafter, the FR-4 copper-clad laminate having a thickness of 1.6 mm was pressed with a vacuum laminator at 60 DEG C under a pressure of 0.5 MPa for 60 seconds to laminate the resin layer of each composition and peel off the PET film. Then, it was cured by heating in a hot air circulation type drying furnace at 180 DEG C for 30 minutes. Then, the copper plating treatment was carried out in the order of permanganic acid dismear (manufactured by ATOTECH), electroless copper plating (through cup PEA, manufactured by Uemura Kogyo Co., Ltd.) and electrolytic copper plating treatment, Respectively. Subsequently, annealing was performed at 190 캜 for 60 minutes in a hot-air circulating type drying furnace to obtain a test substrate subjected to copper plating treatment. Further, it was considered impossible to prepare a composition which had a high viscosity and could not be applied with an applicator.

(Photo-curable resin composition)

Each composition was applied to an FR-4 copper-clad laminate having a thickness of 1.6 mm with an applicator having a gap of 120 탆 and dried in a hot-air circulation type drying oven at 90 캜 for 10 minutes. Thereafter, the dried film was irradiated with a cumulative light quantity of 2000 mJ / cm ² using a conveyor type high-pressure mercury lamp of 120 W / cm. Then, a treatment was conducted in the order of permanganic acid dismear (manufactured by ATOTECH), electroless copper plating (through cup PEA, manufactured by UEMURA KOGYO CO., LTD.) And electrolytic copper plating treatment, and copper plating treatment of copper thickness of 25 μm was carried out on the cured film Respectively. Subsequently, annealing was performed at 190 캜 for 60 minutes in a hot-air circulating type drying furnace to obtain a test substrate subjected to copper plating treatment. Further, it was considered impossible to prepare a composition which had a high viscosity and could not be applied with an applicator.

(Photo-curable thermosetting resin composition)

Each composition was applied to an FR-4 copper-clad laminate having a thickness of 1.6 mm with an applicator having a gap of 120 탆 and dried in a hot-air circulation type drying oven at 90 캜 for 10 minutes. Thereafter, the entire surface transparent mask was closely contacted and exposed at 700 mJ / cm ² using a metal halide lamp exposure apparatus for printed wiring boards. Subsequently, the resist film was developed with a developer of 1 wt% Na ₂ CO ₃ at 30 ° C for 60 seconds. Thereafter, it was cured by heating in a hot air circulation type drying furnace at 150 DEG C for 60 minutes. Then, a treatment was conducted in the order of permanganic acid dismear (manufactured by ATOTECH), electroless copper plating (through cup PEA, manufactured by UEMURA KOGYO CO., LTD.) And electrolytic copper plating treatment, and copper plating treatment of copper thickness of 25 μm was carried out on the cured film Respectively. Subsequently, annealing was performed at 190 캜 for 60 minutes in a hot-air circulating type drying furnace to obtain a test substrate subjected to copper plating treatment. It was impossible to prepare a composition which had a high viscosity and could not be applied with an applicator.

<Measurement of Peel Strength of Plated Copper>

The prepared copper-plated copper sample was cut to a width of 1 cm and a length of 7 cm or more, and the peel strength at an angle of 90 degrees was measured using a 90 ° print peeling jig using a small table tester EZ-SX manufactured by Shimadzu Seisakusho Co., Respectively. The results are shown in Tables 2 to 6.

&Lt; Preparation of Sample for Peel Strength Measurement of Chemical Polished Copper foil >

(Thermosetting resin composition)

(Step 1)

Each composition was applied to a PET film having a thickness of 38 mu m with an applicator having a gap of 120 mu m and dried in a hot air circulation type drying oven at 90 DEG C for 10 minutes to prepare a film in which a resin layer of each composition was formed. Further, it was considered impossible to prepare a composition which had a high viscosity and could not be applied with an applicator.

(Step 2)

The FR-4 copper-clad laminate having a thickness of 1.6 mm was coated with a copper foil (hereinafter simply referred to as &quot; etch-out plate &quot;) with a copper foil completely removed by an etching method using ferric chloride, Four sides of an electrolytic copper foil having a thickness of 18 mu m were fixed with a chemical-resistant adhesive tape. In this state, the electrolytic copper foil is exposed except for the tape adhered portion. Subsequently, an electrolytic copper foil adhered with Etch Bond CZ-8101 manufactured by Mack Co. was chemically polished to prepare a copper foil-attached substrate.

(Step 3)

The resin layer surface of the film produced in the above step 1 was pressed on the copper foil surface of the copper foil-attached substrate produced in the above step 2 with a vacuum laminator at 60 캜 under a pressure of 0.5 MPa for 60 seconds. Thereafter, the PET film was peeled off. Subsequently, the resultant was heated in a hot air circulating type drying oven at 180 DEG C for 30 minutes to cure, thereby preparing a test piece having a cured film of each composition formed on a copper foil of a copper foil-attached substrate.

(Step 4)

A second etch-out plate slightly smaller in four sides than the copper foil of the test piece was adhered to the cured film surface of the test piece prepared in step 3 with a two-liquid epoxy adhesive (Araldite Standard), left at room temperature for 60 minutes, And cured for 5 hours. After the curing, the second etch-out plate adhered to the second etch-out plate was cut with a cutter to remove the first etch-out plate from the first etch-out plate, and the chemically polished copper foil was formed on the cured film of each composition bonded to the second etch- A sample for measuring the peel strength was prepared.

(Photo-curable resin composition)

(Step 1)

The FR-4 copper-clad laminate having a thickness of 1.6 mm was coated with a copper foil (hereinafter simply referred to as &quot; etch-out plate &quot;) with a copper foil completely removed by an etching method using ferric chloride, Four sides of an electrolytic copper foil having a thickness of 18 mu m were fixed with a chemical-resistant adhesive tape. In this state, the electrolytic copper foil is exposed except for the tape adhered portion. Subsequently, an electrolytic copper foil adhered with Etch Bond CZ-8101 manufactured by Mack Co. was chemically polished to prepare a copper foil-attached substrate.

(Step 2)

Each composition was applied to the copper foil-bonded substrate prepared in the above step 1 with an applicator having a gap of 120 탆 and dried at 90 캜 for 10 minutes in a hot air circulation type drying furnace. Thereafter, the test piece was irradiated with a cumulative light quantity of 2000 mJ / cm ² with a conveyer type high-pressure mercury lamp of 120 W / cm to prepare a test piece having a cured film of each composition formed on a copper foil of a copper foil- Further, it was considered impossible to prepare a composition which had a high viscosity and could not be applied with an applicator.

(Step 3)

A second etch-out plate slightly smaller in four sides than the copper foil of the test piece was adhered to the cured film surface of the test piece prepared in the above step 2 with a two-liquid epoxy adhesive (Araldite Standard), left at room temperature for 60 minutes, Lt; 0 &gt; C for 5 hours. After the curing, the second etch-out plate adhered to the second etch-out plate was cut with a cutter to remove the first etch-out plate from the first etch-out plate, and the chemically polished copper foil was formed on the cured film of each composition bonded to the second etch- A sample for measuring the peel strength was prepared.

(Photo-curable thermosetting resin composition)

(Step 1)

The FR-4 copper-clad laminate having a thickness of 1.6 mm was coated with a copper foil (hereinafter simply referred to as &quot; etch-out plate &quot;) with a copper foil completely removed by an etching method using ferric chloride, Four sides of an electrolytic copper foil having a thickness of 18 mu m were fixed with a chemical-resistant adhesive tape. In this state, the electrolytic copper foil is exposed except for the tape adhered portion. Subsequently, an electrolytic copper foil adhered with Etch Bond CZ-8101 manufactured by Mack Co. was chemically polished to prepare a copper foil-attached substrate.

(Step 2)

Each composition was applied to the copper foil-bonded substrate prepared in the above step 1 with an applicator having a gap of 120 탆 and dried at 90 캜 for 10 minutes in a hot air circulation type drying furnace. Thereafter, the entire surface transparent mask was closely contacted and exposed at 700 mJ / cm ² using a metal halide lamp exposure apparatus for printed wiring boards. Subsequently, the resist film was developed with a developer of 1 wt% Na ₂ CO ₃ at 30 ° C for 60 seconds. Thereafter, the resultant was heated in a hot-air circulation type drying furnace at 150 DEG C for 60 minutes to be cured, and a test piece on which a cured film of each composition was formed on a copper foil of a copper foil- Further, it was considered impossible to prepare a composition which had a high viscosity and could not be applied with an applicator.

(Step 3)

A second etch-out plate slightly smaller in four sides than the copper foil of the test piece was adhered to the cured film surface of the test piece prepared in the above step 2 with a two-liquid epoxy adhesive (Araldite Standard), left at room temperature for 60 minutes, Lt; 0 &gt; C for 5 hours. After the curing, the second etch-out plate adhered to the second etch-out plate was cut with a cutter to remove the first etch-out plate from the first etch-out plate, and the chemically polished copper foil was formed on the cured film of each composition bonded to the second etch- A sample for measuring the peel strength was prepared.

&Lt; Peel strength measurement of chemical polishing copper foil &

The sample for peel strength measurement was cut out to a width of 1 cm and a length of 7 cm or more and a peel strength at an angle of 90 degrees was measured using a 90 ° printer peeling jig using a small desk tester EZ-SX manufactured by Shimadzu Seisakusho Co., Respectively. The results are shown in Tables 2 to 6.

&Lt; Peeling of chemical polishing treated copper foil after heat treatment >

A sample with a chemical polishing copper foil prepared was cut to a width of 1 cm and a length of 7 cm or more and dried at 100 ° C for 60 minutes to remove moisture. After drying, the sample was repeatedly subjected to reflow treatment (maximum 270 DEG C) three times, and the presence or absence of peeling of the chemical polishing treated copper foil was visually confirmed. &Quot;, &quot; peeled &quot;, and &quot; x &quot; The results are shown in Tables 2 to 6.

Thermosetting resin 1: Epiclon 830 (bisphenol F type epoxy resin) manufactured by DIC Corporation

Thermosetting resin 2: JER827 (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation

Thermosetting resin 3: EPPN-502H (triphenylmethane type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. (solid content 60% cyclohexanone varnish)

Thermosetting resin 4: FX-293 (Fluorene type phenoxy resin) (manufactured by Shinnitetsu Sumitomo Chemical Co., Ltd. (solid content 30% cyclohexanone varnish)

Thermosetting resin 5: HF-1 (phenol novolac resin) (manufactured by Meiwa Chemical Industries, Ltd.) (solid content 60% cyclohexanone varnish)

Curing catalyst 1: 2E4MZ (2-ethyl-4-methylimidazole) manufactured by Shikoku Chemicals Co.,

Filler 1: Silica, Admapine SO-C2 (manufactured by Admatechs Co., Ltd.)

Filler 2: barium sulfate, B-30 manufactured by Sakai Chemical Industry Co., Ltd.

Organic solvent 1: Dimethylformamide

Antifoaming agent 1: BYK-352 manufactured by Big Chem Japan Co., Ltd.

Photo-curable resin 1: bisphenol A type epoxy acrylate [0154] Mitsubishi Chemical Co., Ltd.

Photocurable resin 2: Trimethylolpropane triacrylate

Photocurable resin 3: Kayama PM2 (hydrogen phosphate = bis [2- (methacryloyloxy) ethyl]) manufactured by Nippon Kayaku Co., Ltd.

Photocurable resin 4: Light ester HO Kyoe Shagaku Co., Ltd.

Photopolymerization initiator 1: 2-Ethylanthraquinone

Colorant 1: Phthalocyanine blue

Curing catalyst 2: fine pulverized melamine manufactured by Nissan Chemical Industries, Ltd.

Curing catalyst 3: Dicyandiamide

Photopolymerization initiator 2: Irgacure 907 manufactured by BASF

Photocurable resin 5: Dipentaerythritol tetraacrylate

Thermosetting resin 6: TEPIC-H (triglycidyl isocyanurate) [0158]

As described in detail above, it is possible to obtain a cellulose-containing microcellulose fiber having an average fiber diameter of not less than 0.1 nm and not more than 200 nm, an average fiber length of not more than 600 nm, and an aspect ratio of not less than 1 but not more than 200 showing a ratio of an average fiber diameter to an average fiber length It has been confirmed that a cured product having low heat expansion and excellent adhesion to a metal conductor can be obtained by using the curable resin composition comprising the hydrophobic microcellulose fiber and the curable resin.

Claims (6)

A resin composition comprising a microcellulose fiber in which a corresponding carboxyl group of a microcellulose fiber having a carboxyl group is hydrophobically modified by at least one of an amine compound and a quaternary ammonium compound and a curable resin,
Wherein the microcellulose fibers having carboxyl groups have an average fiber diameter of not less than 0.1 nm and not more than 200 nm and an average fiber length of not more than 600 nm and an average aspect ratio of not less than 1 and not more than 200. The curable resin composition for printed wiring boards according to claim 1, The curable resin composition for a printed wiring board according to claim 1, further comprising silica. The curable resin composition for a printed wiring board according to claim 1 or 2, wherein the curable resin comprises at least one of a thermosetting resin and a photocurable resin. A dry film having a resin layer formed by applying and drying a curable resin composition for a printed wiring board according to any one of claims 1 to 3 on a film. A cured product obtained by curing the resin layer of the curable resin composition for a printed wiring board according to any one of claims 1 to 3 or the dry film according to claim 4. A printed wiring board comprising the cured product according to claim 5.