CN109565932A

CN109565932A - Printed circuit board hardening resin composition, dry film, solidfied material and printed circuit board

Info

Publication number: CN109565932A
Application number: CN201780048663.2A
Authority: CN
Inventors: 柴田大介; 大川夏芽; 宇敷滋; 三轮崇夫; 大和恭平; 熊本吉晃
Original assignee: Kao Corp; Taiyo Holdings Co Ltd
Current assignee: Kao Corp; Taiyo Holdings Co Ltd
Priority date: 2016-08-09
Filing date: 2017-08-09
Publication date: 2019-04-02
Also published as: KR20190050980A; JP2018024878A; TW201817783A; WO2018030465A1

Abstract

Low heat expansion, printed circuit board hardening resin composition, dry film, solidfied material and printed circuit board with the good solidfied material of adaptation of metallic conductor can be obtained by providing.Resin combination includes fine cellulose fiber and curable resin, and the fine cellulose fiber is that the carboxyl of the fine cellulose fiber with carboxyl is modified using at least any one in amine compounds and quaternary ammonium compound come made of hydrophobization.Fine cellulose fiber with carboxyl, avarage fiber diameter is 0.1nm or more and 200nm or less, average fiber length are 600nm or less and average aspect ratio is 1 or more and 200 or less.

Description

Printed circuit board hardening resin composition, dry film, solidfied material and printed circuit board

Technical field

The present invention relates to the printed circuit board hardening resin compositions comprising the fine cellulose fiber through hydrophobization (hereinafter, also referred to as " hardening resin composition "), dry film, solidfied material and printed circuit board.

Background technique

Printed circuit board is to implement the wiring of electric conductor to insulating substrate, by the electronic component person of being connected and fixed, depending on the application, Sometimes make insulating layer and conductor layer multiple stratification or use flexible insulating substrate, become important portion in the electronic device Part.In addition, printed circuit board is also used for semiconductor package body, printed circuit board hardening resin composition, dry film are used as Outer layer after wiring plate, semiconductor installation.

In recent years, with the miniaturization of electronic equipment, the densification of wiring is required printed circuit board, in order to ensure cloth The reliability of line, component interconnecting piece, the thermal expansivity low to the material requirements of printed circuit board.

As the method for reaching low heat expansion, for example, patent document 1,2 proposes use for fine cellulose fiber point The method of material made of dissipating in composition.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2011-001559 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2012-119470 bulletin

Summary of the invention

Problems to be solved by the invention

But the material for being recorded in patent document 1,2, there are adaptation differences of metallic conductor etc., and reliability to be caused to drop Low problem.

Therefore, the object of the present invention is to provide can obtain low heat expansion, it is good with the adaptation of metallic conductor Printed circuit board hardening resin composition, dry film, solidfied material and the printed circuit board of solidfied material.

The solution to the problem

The inventors of the present invention have made intensive studies, as a result, it has been found that, by using by avarage fiber diameter be specific range, Average fiber length is that the draw ratio of the ratio between particular value or less, expression avarage fiber diameter and average fiber length is specific model Substance made of fine cellulose fiber hydrophobization enclose, with carboxyl, is able to solve the above problem, so as to complete this hair It is bright.

That is, printed circuit board hardening resin composition of the invention is characterized in that, the resin combination includes Fine cellulose fiber and curable resin, the fine cellulose fiber are the carboxylics of the fine cellulose fiber with carboxyl Base is modified using at least any one in amine compounds and quaternary ammonium compound come made of hydrophobization,

The aforementioned fine cellulose fiber with carboxyl, avarage fiber diameter be 0.1nm or more and 200nm or less, it is flat Equal fibre length is 600nm or less and average aspect ratio is 1 or more and 200 or less.

Resin combination of the invention preferably also includes silica.In addition, resin combination of the invention preferably comprises At least any one in heat-curing resin and light-cured resin is as said curing property resin.

Dry film of the invention is characterized in that, thin with above-mentioned printed circuit board to be coated on hardening resin composition On film and resin layer made of drying.

Solidfied material of the invention is characterized in that, be by the solidification of above-mentioned printed circuit board hardening resin composition and At or made of the aforementioned resin layer of above-mentioned dry film solidified.

Printed circuit board of the invention is characterized in that having above-mentioned solidfied material.

The effect of invention

According to the present invention, it can be achieved that the good solidfied material of adaptation of low heat expansion and metallic conductor can be obtained Printed circuit board hardening resin composition, dry film, solidfied material and printed circuit board.

Specific embodiment

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

Printed circuit board of the invention hardening resin composition includes fine cellulose fiber and curable resin, institute Stating fine cellulose fiber is the carboxyl of the fine cellulose fiber with carboxyl using in amine compounds and quaternary ammonium compound At least any one, which is modified, comes made of hydrophobization, straight using average fiber as the fine cellulose fiber with carboxyl Diameter is 0.1nm or more and 200nm or less, average fiber length are 600nm or less and average aspect ratio (average fiber length/ Avarage fiber diameter) it is 1 or more and 200 fine cellulose fibers below with carboxyl.

Herein, for the fine cellulose fiber with carboxyl, avarage fiber diameter is 0.1nm or more and 200nm or less, Average fiber length is 600nm or less and average aspect ratio is 1 or more and 200 hereinafter, for the microfibre with carboxyl The carboxyl of cellulose fiber is modified fine cellulose fiber made of carrying out hydrophobization, and avarage fiber diameter is 0.1nm or more And 200nm or less, average fiber length are 600nm or less and average aspect ratio is 1 or more and 200 or less.

Hereinafter, the fine cellulose fiber with carboxyl is also referred to as contained carboxyl fine cellulose fiber, it is micro- carboxyl will to be contained Fine cellulose fiber made of the carboxyl hydrophobization of fine cellulose fiber is also referred to as hydrophobization fine cellulose fiber.

In the past, exist and the fine cellulose fiber containing carboxyl usually with 300 or so average aspect ratio is combined The silicic acid anhydride of various modification groups etc., although the fine cellulose fiber is low heat expansion, but and metallic conductor Adaptation it is low.

But the inventors of the present invention have found, according to comprising being 1 or more and 200 below micro- containing carboxyl to average aspect ratio Fine cellulose fiber implements the composition of silicic acid anhydride and winner and curable resin, the then solidfied material obtained by the composition In the case where maintaining low heat expansion, it is also excellent with the adaptation of metallic conductor.

The detailed reason for playing such effect is indefinite, but speculates are as follows: since average aspect ratio is included in above range In fine cellulose fiber containing carboxyl be that the fragile part such as non-crystalline areas that will be present in native cellulose fibre is cut Break and carry out staple fiber and winner, therefore the distribution proportion of crystal region increases as a whole, therefore is staple fiber, and can Maintain low heat expansion.

It is additionally contemplated that since the fibre length of obtained hydrophobization fine cellulose fiber is also short, in resin combination Dispersibility in object improves, to also give full play to the effect as filler, therefore low heat expansion is excellent and leads with metal The adaptation of body is also excellent.

Hardening resin composition of the invention is suitable for forming the insulating layer of printed circuit board, such as suitable for shape The sealers such as sandwich layer, interlayer insulating film, solder mask at printed circuit board.

In addition, as hardening resin composition of the invention, for example, the thermosetting comprising heat-curing resin can be enumerated The property changed resin combination, includes light-cured resin and heat cure at the Photocurable resin composition comprising light-cured resin The light solidifying/heat solidifying resin composition of property resin.

(hydrophobization fine cellulose fiber)

Above-mentioned hydrophobization fine cellulose fiber is that the carboxyl of the fine cellulose fiber containing carboxyl utilizes amine compounds and season At least any one in ammonium compounds is modified to come made of hydrophobization, can be obtained as follows.

As the native cellulose fibre of raw material, such as the wood such as coniferous tree system paper pulp, broad leaf tree system paper pulp can be enumerated Material paper pulp；The cotton system paper pulp of cotton linters, gined cotton (cotton lint) etc；The non-timbers such as wheat straw paper pulp, begasse pulp system paper Slurry；Bacteria cellulose etc., these can be used alone or two or more is applied in combination.

Above-mentioned raw material are mainly made of cellulose, hemicellulose and lignin, wherein the content of lignin be usually 0~ 40 mass % or so, especially for 0~10 mass % or so.As needed, lignin can be carried out to these raw material to go It removes and/or bleaching is to carry out the adjustment of lignin amount.It should be noted that the measurement of content of lignin can pass through Klason method carries out.

In the cell wall of plant, cellulosic molecule not instead of unimolecule is regularly assembled and is collected so as to form tens That closes has crystalline microfibril, this becomes the basic framework material of plant.Therefore, micro- in order to be manufactured by above-mentioned raw material Fine cellulose fiber implements mashing and/or pulverization process to above-mentioned raw material, high-temperature high-pressure steam processing, utilizes phosphate Deng processing etc., so as to unlock its fiber to nano-scale.

In addition, by carrying out oxidation processes (for example, having used at the oxidation of aftermentioned TEMPO to native cellulose fibre Manage) primary hydroxyl of the position C6 in the glucopyra saccharide ring of native cellulose is selectively oxidized to carboxyl, it can be contained Carboxylated fiber cellulose fiber.By carrying out the processing, cellulose fibre can be unlocked to nano-scale with weaker shearing force.

In turn, at least one of amine compounds and quaternary ammonium compound are utilized by the way that the carboxyl of carboxylated fiber cellulose fiber will be contained It is modified and carrys out hydrophobization, above-mentioned hydrophobization fine cellulose fiber can be obtained.

Hereinafter, the manufacturing method to hydrophobization fine cellulose fiber used in the present invention is specifically recorded.

(slurried process)

Firstly, preparation be dispersed in water native cellulose fibre made of slurry.For slurry, by as raw material Native cellulose fibre (adiabatic drying benchmark: the matter of the native cellulose fibre at 150 DEG C after heat drying 30 minutes Amount) about 10~1000 times of water for measuring (quality criteria) are added, it is handled with mixer etc. to obtain.It can be to native cellulose Fiber implements mashing etc. for improving the processing of surface area.In addition, the cellulose I type crystallinity of above-mentioned commercially available paper pulp is usually 80% or more.

(oxidation processes process)

Then, oxidation processes are carried out in the presence of the oxidants such as N- oxo-compound to above-mentioned native cellulose fibre, Obtain cellulose fiber containing carboxylated fiber (hereinafter, being also referred to as " oxidation processes " sometimes).

As N- oxo-compound, it is preferably selected from piperidines oxo-compound, the pyrroles's alcoxyl of the alkyl with carbon number 1 or 2 The N- oxo-compound of one or more of based compound, imidazoline oxo-compound and azaadamantane compound hetero ring type. In these, from the viewpoint of reactivity, preferably there is the piperidines oxo-compound of the alkyl of carbon number 1 or 2,2 can be enumerated, 2,6,6- tetraalkyl piperidine -1- nitrogen oxides (TEMPO), 4- hydroxyl -2,2,6,6- tetraalkyl piperidine -1- nitrogen oxides, 4- alkane Oxygroup -2,2,6,6- tetraalkyl piperidine -1- nitrogen oxides, 4- benzoyloxy -2,2,6,6- tetraalkyl piperidine -1- nitrogen oxidation The two tertiary alkyl oxynitrides, 4- acetamide-TEMPO, 4- such as object, 4- amino -2,2,6,6- tetraalkyl piperidine -1- nitrogen oxides Carboxyl-TEMPO, 4- phosphonato-TEMPO etc..In these piperidines oxynitrides, more preferable 2,2,6,6- tetramethyl piperidines- 1- nitrogen oxides (TEMPO), 4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- nitrogen oxides, 4- methoxyl group -2,2,6,6- tetramethyl Phenylpiperidines -1- nitrogen oxides, further preferred 2,2,6,6- tetramethyl piperidine -1- nitrogen oxides (TEMPO).

For the amount of N- oxo-compound, as long as being catalytic amount, relative to native cellulose fibre (adiabatic drying Benchmark) 100 mass parts, preferably 0.001~10 mass parts, more preferably 0.01~9 mass parts, further preferred 0.1~8 matter It measures part, be still more preferably 0.5~5 mass parts.

In the oxidation processes of native cellulose fibre, the oxidant in addition to N- oxo-compound can be used.As oxygen Agent can enumerate oxygen or air, mistake from the viewpoint of solubility, reaction speed when solvent is adjusted to alkaline domain etc. Oxide；Halogen, hypohalogenous acids, halous acid, high hydracid and their alkali metal salt or alkali salt；Halogen oxide, nitrogen oxygen Compound etc..In these, preferred as alkali hypohalite, specifically, sodium hypochlorite, sodium hypobromite can be exemplified.Oxidant Dosage selected according to the carboxyl degree of substitution (oxidizability) of native cellulose fibre, in addition, due to oxidation reaction yield It is different according to reaction condition, therefore cannot entirely determine, it is (absolutely dry relative to the native cellulose fibre as raw material Dry benchmark) 100 mass parts, the preferably from about range of 1~100 mass parts.

In addition, as co-catalyst, sodium bromide, bromine can be used in order to which further efficiency carries out oxidation reaction well Change iodide such as bromides, sodium iodide, the potassium iodide such as potassium etc..For the amount of co-catalyst, as long as its function can be played Effective quantity is not particularly limited.

For the reaction temperature in oxidation processes, from the viewpoint of the selectivity of reaction, inhibition side reaction, preferably 50 DEG C or less, more preferably 40 DEG C or less, further preferably 20 DEG C hereinafter, its lower limit preferably -5 DEG C or more.

In addition, be preferably consistent with the property of oxidant for the pH of reaction system, for example, use sodium hypochlorite as In the case where oxidant, the pH of reaction system is preferably set to alkalinity, preferably pH7~13, more preferable pH10~13.In turn, it reacts Time preferably 1~240 minute.

By carrying out above-mentioned oxidation processes, obtaining carboxyl-content is preferably the fine containing carboxycellulose of 0.1mmol/g or more Dimension.

(purification procedures)

Fiber containing carboxycellulose obtained in above-mentioned oxidation processes process includes the N- such as the TEMPO used as catalyst Oxo-compound, by-product salt.Subsequent processing can be directly carried out, purifying can also be carried out to obtain the fine containing carboxyl of purity is high Cellulose fiber.As purification process, the type of the solvent in oxidation reaction, the degree of the oxidation of product, purifying can be passed through Degree uses optimal method.Use water as good solvent for example, can enumerate, use methanol, ethyl alcohol, acetone etc. as not The ion exchange of the extraction and salt in the solvent that hexane etc. can be separated mutually with water such as reprecipitation, TEMPO of good solvent is based on The purifying etc. of dialysis etc..

(miniaturization process)

Then, the process being miniaturize to obtained cellulose fiber containing carboxylated fiber is carried out after above-mentioned purification procedures.It is micro- In refinement, it is scattered in the cellulose fiber containing carboxylated fiber that have passed through above-mentioned purification procedures in solvent, is miniaturize Processing.By carrying out the miniaturization process, to obtain the fine cellulose fiber that average aspect ratio is in above range.

As the solvent of decentralized medium, in addition to water, carbon numbers such as methanol, ethyl alcohol, propyl alcohol 1~6, preferably can be also exemplified The alcohol of carbon number 1~3；The ketone of the carbon numbers such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) 3~6；The carbon number 1~6 of straight or branched Saturated hydrocarbons or unsaturated hydrocarbons；The aromatic hydrocarbons such as benzene, toluene；The halogenated hydrocarbons such as methylene chloride, chloroform；The low alkyl group of carbon number 2~5 Ether；N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, succinic acid and triethylene glycol monomethyl ether diester Isopolarity solvent etc..These may be used alone or in combination two or more, go out from the viewpoint of the operability of miniaturization processing Hair, preferably water, the alcohol of carbon number 1~6, the ketone of carbon number 3~6, the lower alkyl ether of carbon number 2~5, n,N-Dimethylformamide, N, N- dimethyl acetamide, dimethyl sulfoxide, amber acid methyl triethylene glycol diester isopolarity solvent, from the sight for reducing environmental pressure Point sets out, more preferable water.For the dosage of solvent, as long as the effective quantity that can disperse cellulose fiber containing carboxylated fiber, It is not particularly limited, it can be to be preferably 1~500 mass times, more preferably 2~200 matter relative to cellulose fiber containing carboxylated fiber Amount uses again.

As device used in miniaturization processing, well known dispersion machine can be suitably used.It is, for example, possible to use solutions It disembarks, beater, low pressure homogenizer, high pressure homogenizer, grinder, shredding machine (cutter mill), ball mill, aeropulverizer, list Screw extruder, double screw extruder, ultrasonic stirrer, home-use juice extractor mixer etc..In addition, in miniaturization processing React the solid component concentration preferably 50 mass % or less of fibres.

In addition, can take a step forward and be carried out at biochemical treatment, chemistry in the above-mentioned miniaturization processing of progress in the present invention At least one kind of processing of reason and mechanical treatment.Specifically, sour water solution, hot water decomposition, oxygenolysis, crushing, enzyme can be enumerated The processing methods such as processing, UV processing, electron beam treatment handle the staple fiber, it can be achieved that cellulose fibre by these, thus It can be more effectively carried out miniaturization processing, and then average aspect ratio includes within the above range.As above-mentioned process content, example Such as, the method that the cellulose fiber containing carboxylated fiber that have passed through purification procedures flows back in acid can be enumerated.The type and its dense of acid Degree is not particularly limited.For example, addition concentrated hydrochloric acid can be exemplified, the cellulose fiber containing carboxylated fiber for being 0.1~10M to concentration of hydrochloric acid The method that is heated of aqueous dispersions.

As the form of obtained fine cellulose fiber, as needed, it can also be made and have adjusted solid component concentration Suspension liquid (being visually colorless and transparent or opaque liquid) or powdered (wherein, for microfibre through what is be dried It is powdered made of cellulose fiber aggregation, do not refer to cellulose grain).It should be noted that making in the case where suspension liquid is made For decentralized medium, water can be used only, water and other organic solvents (for example, the alcohols such as ethyl alcohol), surface-active also can be used The mixed solvent of agent, acid, alkali etc..

Operated as described above, the hydroxyl of the position C6 of cellulosic structure unit is selectively oxidized to via aldehyde radical Carboxyl, can obtain above-mentioned carboxyl-content be 0.1mmol/g or more and avarage fiber diameter be 0.1~200nm, average fibre Dimension length is 600nm or less, average aspect ratio be 1 or more and 200 celluloses below through miniaturizeing, preferably have 30% with On crystallinity fine cellulose fiber.

(avarage fiber diameter, average fiber length and the average aspect ratio of fine cellulose fiber)

It, can be with for avarage fiber diameter, average fiber length and the average aspect ratio of the fine cellulose fiber containing carboxyl It measures as follows.

To water is added in fine cellulose fiber containing carboxyl, the dispersion liquid that its concentration is 0.0001 mass % is prepared, it will be The dispersion liquid is added dropwise and drying on mica (mica) and winner as observation sample, using atomic force microscope (AFM, Nanoscope III Tapping mode AFM, Digital instrument corporation, probe use Nano sensors Corporation Point Probe (NCH)), the fiber height of the fine cellulose fiber in sample is observed in measurement.At this point, can Confirm and extract 5 or more fine cellulose fibers in the MIcrosope image of fine cellulose fiber, is calculated by these fiber heights Avarage fiber diameter.In addition, calculating average fiber length according to the distance of machine direction.Average aspect ratio is by average fibre Tie up what length/avarage fiber diameter calculated.

In the present invention, the avarage fiber diameter of the fine cellulose fiber containing carboxyl is 0.1nm or more and 200nm is hereinafter, excellent Be selected as 1nm or more and 100nm or less, more preferably 2nm or more and 50nm or less, further preferred 2.5nm or more and 20nm with Under.It is difficult to the fine cellulose fiber containing carboxyl for manufacturing avarage fiber diameter less than 0.1nm, in addition, if avarage fiber diameter is super 200nm is crossed, then cannot obtain the good solidfied material of conductor adaptation with printed circuit board.

The average fiber length of the fine cellulose fiber containing carboxyl be 600nm hereinafter, preferably 50nm or more and 600nm with Under, more preferably 100nm or more and 500nm or less, further preferably 150nm or more and 500nm or less.Average fiber length Become difficult more than dispersion of the 600nm person when composition is made.

The average aspect ratio of the fine cellulose fiber containing carboxyl be 1 or more and 200 hereinafter, preferably 5 or more and 180 with Under, more preferably 9 or more and 170 or less, particularly preferably 9 or more and less than 100.It is difficult to manufacture average aspect ratio less than 1 Fine cellulose fiber containing carboxyl cannot obtain and the good solidification of metallic conductor adaptation if average aspect ratio is more than 200 Object.If average aspect ratio be 200 hereinafter, if the adaptation of metallic conductor and solidfied material it is good, average aspect ratio is smaller, and metal is led The adaptation of body and solidfied material is more excellent, more can reduce the viscosity of composition.

In the present invention, modification is carried out to the fine cellulose fiber of hydrophobization using to above-mentioned carboxyl.That is, using utilizing The hydrophobization fine cellulose that amine compounds, quaternary ammonium compound modify the fine cellulose fiber with carboxyl is fine Dimension.

Hereinafter, being illustrated to the hydrophobization fine cellulose fiber.

The carboxyl of the fine cellulose fiber containing carboxyl is modified to come in fine cellulose fiber made of hydrophobization, modification Group is bonded to cellulosic backbone by any one of amido bond or amine salt or both.

As modification group, as long as being for the functional group being bonded by any one of amido bond or amine salt or both Can, for example, the alkyl of the alkyl of carbon number 1 or the saturations or undersaturated straight chain shape of carbon number 2~30 or branched can be enumerated. As concrete example, alkyl below can be enumerated.

The alkyl of carbon number 1: methyl.

The alkyl of the straight-chain of the saturation of carbon number 2~30: ethyl, propyl, butyl, amyl, hexyl, octyl, nonyl, the last of the ten Heavenly stems Base, dodecyl, octadecyl, docosyl, octacosyl.

The alkyl of the unsaturated straight-chain of carbon number 2~30: oil base, myristoyl base, palmityl, sub- oleyl alcohol base, flax Alcohol radical, eicosyl.

The alkyl of the branched of the saturation of carbon number 2~30: isopropyl, isobutyl group, sec-butyl, tert-butyl, isopentyl, uncle penta Base, isohesyl, 2- hexyl, dimethylbutyl, ethyl-butyl.

For the carbon number of the alkyl of saturations or undersaturated straight chain shape or branched, according to the combination with curable resin come Any selection, preferably 1 or more, particularly 3 or more, especially 10 or more, it is additionally preferred to for 30 or less, particularly 20 or less, Especially 18 or less.For example, it is preferable to for 1 or more and 30 or less, preferably 3 or more and 20 or less, be still more preferably 10 with It is upper and 18 or less.By making carbon number be in above-mentioned range, so that fine cellulose fiber and curable resin are in uniform mixed The good physical property as resin combination such as low coefficient of linear thermal expansion can be obtained in conjunction state.

As the amine with above-mentioned saturations or undersaturated straight chain shape or the alkyl of branched, specifically, as primary amine, For example, can enumerate methylamine, ethamine, propylamine, isopropylamine, butylamine, hexylamine, octylame, decyl amine, lauryl amine, octadecylamine, The monoalkylamines such as oleyl amine.As secondary amine, for example, dimethylamine, diethylamine, dibutyl amine, two (octadecyl) amine etc. two can be enumerated Alkylamine.

In addition, total carbon number is 6~20 as the amine with aromatic hydrocarbyl, it can be any in primary amine, secondary amine Person, from the viewpoint of the reactivity with carboxyl, preferred primary amine.In addition, for the quantity of the aromatic hydrocarbyl in amine, total carbon number It can be any one in 1,2 when being 6~20, preferably 1.

As the amine with aromatic hydrocarbyl, the amine with aryl, the amine with aralkyl can be enumerated, from resin From the perspective of compatibility, preferably with the amine of aryl.

As aryl, specifically, phenyl, naphthalene, anthryl, phenanthryl, xenyl, triphenyl can be enumerated, these can be with Individually or two or more is combined.Wherein, from the viewpoint of the compatibility with resin, preferably phenyl, naphthalene, xenyl, more preferably Phenyl.

As aralkyl, specifically, benzyl, phenethyl, phenyl propyl, phenylpentyl, Phenylhexyl, benzene can be enumerated Base heptyl, these can individually or two or more is combined.Wherein, from the viewpoint of the compatibility with resin, preferably benzyl, benzene Ethyl, phenyl propyl, phenylpentyl, Phenylhexyl, more preferable benzyl, phenethyl, phenyl propyl, phenylpentyl.

In addition, above-mentioned aryl, aralkyl can have substituent group, as substituent group, for example, can enumerate methyl, ethyl, The alkyl of the carbon numbers such as propyl, isopropyl, butyl, isobutyl group, sec-butyl, tert-butyl, amyl, isopentyl, hexyl 1~6；Methoxy Base, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, amoxy, isoamoxy, The alkoxy of the carbon numbers such as hexyloxy 1~6；Methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, isopropoxy carbonyl, butoxy The carbon numbers 1~6 such as carbonyl, isobutoxy carbonyl, s-butoxycarbonyl, tert-butoxycarbonyl, pentyloxy carbonyl, isoamoxy carbonyl Alkoxy carbonyl；The halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom；Acyl group, aralkyl, the aralkyl of carbon number 1~6 Base oxygroup.

As the amine with above-mentioned aromatic hydrocarbyl, specifically, aniline, first can be enumerated as the amine with aryl Aniline, 4- benzidine, diphenylamine, 2- amino naphthalenes, para-terpheny amine, 2- amino anthracene, 2- amino anthraquinones.Wherein, from resin Compatibility from the perspective of, preferably aniline, toluidines, 4- benzidine, diphenylamine, 2- amino naphthalenes, more preferable aniline.As Amine with aralkyl can enumerate benzylamine, phenyl ethylamine, 3- phenyl propyl amine, 5- phenylpentyl amine, 6- Phenylhexyl amine, 7- Phenylheptylamine, 8- phenyl octyl amine.Wherein, from the same viewpoint, preferably benzylamine, phenyl ethylamine, 3- phenyl propyl amine, 5- Phenylpentyl amine, 6- Phenylhexyl amine, 7- phenylheptylamine, more preferable benzyl amine, phenethyl amine, 3- phenyl propyl amine, 5- benzene Base amylamine, 6- Phenylhexyl amine, further preferred benzylamine, phenyl ethylamine, 3- phenyl propyl amine, 5- phenylpentyl amine.The present invention Used in can be prepared according to known methods with the amine of aromatic hydrocarbyl, or commercially available product.

In addition, in addition to this, for after the ethylene oxide, propylene oxide of addition desired amount on propylene glycol alkyl ether by hydroxyl Amine made of base terminal amino group, the amine with hydrophilic groups such as hydroxyethyl, hydroxypropyls gather with ethylene glycol, propylene glycol etc. The polyester chains such as ether chain, lactide, caprolactone, polyetheramine, polyesteramine, the amine with alicyclic type hydrocarbons such as cyclopenta, cyclohexyl, It can also function properly as in hydrophobization fine cellulose fiber used in the present invention by any in amido bond or amine salt Person or both and be bonded compound.

It, can as the quaternary ammonium compound for being modified and being formed amine salt for the carboxyl to hydrophobization fine cellulose fiber Enumerate tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrabutylammonium hydroxide, tetrapropylammonium hydroxide, tetraethyl chlorination Ammonium, tetrabutylammonium chloride, lauryl trimethyl ammonium chloride, dilauryl ammonium chloride, stearyl trimethyl ammonium chloride, two Stearyldimethylammonium chloride, cetyl trimethyl ammonium chloride, alkyl benzyl dimethyl ammonium chloride.Wherein, it is repaired to carboxyl From the perspective of the easness of decorations, preferably tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, the tetrabutyl Ammonium hydroxide.

For the additive amount of the hydrophobization fine cellulose fiber in hardening resin composition of the invention, relative to solid Total amount (solid component benchmark) 100 mass parts of the property changed resin, more than preferably 0.1 mass parts and 30 below the mass, more excellent It is selected as 1 mass parts or more and 20 below the mass, more than further preferably 2 mass parts and 10 below the mass.If by adding Amount is set as 0.1 mass parts or more, then thermal expansivity is low, if being set as 30 below the mass, low heat expansion and metallic conductor The balance of adaptation is excellent.

(method of modifying of the carboxyl of fine cellulose fiber)

The method of modifying of carboxyl as the fine cellulose fiber in the present invention can enumerate the following method.

As the 1st method, it can enumerate and send as an envoy to fine cellulose fiber containing carboxyl and the amine compounds with modification group exist The method salt is made is mixed in solvent.

The dosage of above-mentioned amine compounds is determined according to the bonded amount of the desired amine salt in hydrophobization fine cellulose fiber Fixed, relative to carboxyl 1mol contained in fine cellulose fiber containing carboxyl, amino is preferably 0.1mol or more, is more preferably 0.5mol or more, further preferably 0.7mol or more, it is still more preferably 1mol or more, goes out from the viewpoint of product purity Hair uses preferably 50mol or less, more preferably 20mol or less, further preferably 10mol amount below.It needs to illustrate It is that can be included within the amine of the amount in above range disposably for salt formation process, work can also be formed for salt in batches Sequence.

As solvent, the solvent that the amine compounds used can dissolve is preferably selected, for example, ethyl alcohol, isopropanol can be enumerated (IPA), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), DMAC N,N' dimethyl acetamide, tetrahydrofuran (THF), The diester of succinic acid and triethylene glycol monomethyl ether, acetone, methyl ethyl ketone (MEK), acetonitrile, methylene chloride, chloroform, toluene, acetic acid etc., These can be used alone or two or more is applied in combination.In these polar solvents, preferably succinic acid and triethylene glycol list first Diester, ethyl alcohol, the DMF of ether.

Temperature when mixing is preferably 0 DEG C or more, more preferably 5 DEG C or more, further preferably 10 DEG C or more.In addition, From the viewpoint of the coloring of hydrophobization fine cellulose fiber, preferably 50 DEG C or less, more preferably 40 DEG C or less, further Preferably 30 DEG C or less.Incorporation time can be suitable for setting according to the type of the amine and solvent that use, and preferably 0.01 hour Above, be more preferably 0.1 hour or more, further preferably 1 hour or more, preferably 48 hours or less, be more preferably it is 24 small When below, further preferably 12 hours or less.

It can be suitable for being post-processed to remove the not used amine compounds of the formation of salt after the formation of above-mentioned salt. As the method for the post-processing, it is, for example, possible to use filtering, centrifuge separation, dialysis etc..

As the 2nd method, the fine cellulose fiber sent as an envoy to carboxyl and the amine compounds with modification group can be enumerated The method of object amidation process in a solvent.

The dosage of amine compounds with above-mentioned modification group can pass through the expectation in hydrophobization fine cellulose fiber Bonded amount determine, from the viewpoint of reactivity, relative to carboxyl contained in fine cellulose fiber containing carboxyl 1mol, amino are preferably 0.1mol or more, more preferably 0.5mol or more, are more preferably 0.7mol or more, further Preferably 1mol or more, from the viewpoint of product purity, using preferably 50mol or less, more preferably 20mol or less, into One step is preferably 10mol amount below.It should be noted that the amine for the amount that can be included in above range disposably for Reaction, can also be in batches for reaction.

Public affairs also can be used in above-mentioned fine cellulose fiber containing carboxyl and the reacting of amine compounds with modification group The condensing agent known.

As condensing agent, be not particularly limited, can enumerate synthesis chemical series peptide synthesis (Wan Shan company) P116 record, Or Tetrahedron, the condensing agent etc. recorded in 57,1551 (2001), for example, can enumerate 4- (4,6- dimethoxy -1, 3,5- triazine -2- bases) -4- methylmorpholinium chloride (hereinafter, otherwise referred to as " DMT-MM ") etc..

In above-mentioned condensation reaction, the solvent that the amine compounds used can dissolve is preferably selected.

The reaction time of above-mentioned condensation reaction and reaction temperature can be suitable for according to type of the amine and solvent that use etc. Selection, from the viewpoint of reactivity and productivity, preferably 1~24 hour, more preferably 10~20 hours.In addition, from anti- From the perspective of answering property, reaction temperature is preferably 0 DEG C or more, more preferably 5 DEG C or more, further preferably 10 DEG C or more.Separately Outside, from the viewpoint of the coloring of hydrophobization fine cellulose fiber, preferably 200 DEG C or less, more preferably 80 DEG C or less, into One step is preferably 30 DEG C or less.

It can be suitable for carrying out to remove unreacted amine compounds, condensing agent etc. after above-mentioned mixing and after reaction Post-processing.As the method for the post-processing, it is, for example, possible to use filtering, centrifuge separation, dialysis etc..

As the 3rd method, the fine cellulose fiber with carboxyl and with the quaternized of modification group of sening as an envoy to can be enumerated It closes object and mixes the method salt is made in a solvent.

The dosage of above-mentioned quaternary ammonium compound can determine according to the desired bonded amount in hydrophobization fine cellulose fiber Fixed, relative to carboxyl 1mol contained in fine cellulose fiber containing carboxyl, quaternary ammonium cation is preferably 0.1mol or more, more It preferably 0.5mol or more, further preferably 0.7mol or more, is still more preferably 1mol or more, from the sight of product purity Point sets out, and uses preferably 50mol or less, more preferably 20mol or less, further preferably 10mol amount below.It needs It is bright, the quaternary ammonium compound of the amount in above range can be included within disposably for the formation process of salt, can also be divided Criticize the formation process for salt.

As solvent, it can be used in the same manner solvent used when mixing with above-mentioned amine, in addition it is also possible to use water.It Can be used alone or two or more is applied in combination, wherein preferred water, the diester of succinic acid and triethylene glycol monomethyl ether, second Alcohol, DMF.

Temperature, time and salt when for mixing formed after post-processing, referring to the feelings that are mixed with above-mentioned amine compounds Condition can be suitable for setting.

(curable resin)

Hardening resin composition of the invention is that hot curing resin composition, Photocurable resin composition or light are solid The property changed hot curing resin composition.

(hot curing resin composition)

Hot curing resin composition of the invention preferably comprises heat-curing resin, inorganic filler and curing catalysts.

As heat-curing resin used in hot curing resin composition, it is generally desirable to can be into using heat using having The resin of the functional group of row curing reaction, particularly preferably using has 1 compound with upper annular (sulphur) ether in molecule.

As the compound with cyclic ether group, for example, bisphenol A type epoxy resin, bisphenol F type epoxy tree can be enumerated Rouge, bisphenol-s epoxy resin, bisphenol E-type epoxy resin, bis-phenol M type epoxy resin, bis-phenol p-type epoxy resin, bisphenol Z type ring The bisphenol-type epoxy resins such as oxygen resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, phenol novolak type epoxy resin, cresols phenol The phenolic resin varnish type epoxy resins such as Novolac epoxy resin, biphenyl type epoxy resin, xenyl aralkyl-type epoxy resin, virtue Base alkylene type epoxy resin, four phenolic group ethane type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, phenoxy group type ring Oxygen resin, dicyclopentadiene-type epoxy resin, norbornene-type epoxy resin, adamantane type epoxy resin, fluorenes type epoxy resin, Glycidyl methacrylate copolymerization is being total to for epoxy resin, N-cyclohexylmaleimide and glycidyl methacrylate Poly epoxy resin, epoxy-modified polybutadiene rubber derivative, CTBN modified epoxy, trimethylolpropane bunching water are sweet Oily ether, phenyl -1,3- diglycidyl ether, xenyl -4,4 '-diglycidyl ether, 1,6- hexane diol diglycidyl ether, Ethylene glycol or the diglycidyl ether of propylene glycol, d-sorbite polyglycidyl ether, three (2,3- glycidyl) isocyanuric acid esters, The epoxy resin such as triglycidyl group three (2- hydroxyethyl) isocyanuric acid ester；Phenol resol resins, cresol novolak The novolak phenolics such as resin, bisphenol A novolac resin, unmodified resol, with tung oil, linseed The phenolic resin such as the resol type phenol resins such as the modified resol of the oil that oil, walnut oil etc. are modified；Phenoxy group tree Rouge；Urea (urea) resin；The resin containing triazine ring such as melamine resin；Unsaturated polyester resin, diallyl phthalate third Ester resin, organic siliconresin, the resin with benzoxazine ring, norbornene resin, cyanate ester resin, isocyanates tree Rouge, carbamate resins, benzocyclobutane olefine resin, maleimide resin, bismaleimide-triazine resin, poly methylene imine Resin, Thermocurable polyimides, cyanate ester resin, active ester resin etc..

As heat-curing resin, it is generally desirable to include epoxy resin and phenolic resin.By the inclusion of epoxy resin and phenol Urea formaldehyde, so as to improve heat resistance, peel strength and insulating reliability etc..As the content of epoxy resin, relative to complete 100 mass parts of portion's heat-curing resin, more than for example, 1 mass parts and 90 below the mass, it is more than preferably 10 mass parts and 85 below the mass, more preferably more than 20 mass parts and 80 below the mass.As the content of phenolic resin, relative to whole Heat-curing resin, more than for example, 1 mass parts and 70 below the mass, more than preferably 5 mass parts and 60 below the mass, More than more preferably 10 mass parts and 50 below the mass.

In addition, use active ester resin as in the case where heat-curing resin, if using dimethyl aminopyridine, it can Enough improve curability.

In the hardening resin composition of the present application, by the way that fine cellulose fiber and inorganic filler is applied in combination, To the reduction excellent effect of the linear expansion coefficient of solidfied material.

As inorganic filler, barium sulfate, barium titanate, amorphous silica, crystallinity silica, melting can be enumerated Silica, spherical silicon dioxide, talcum, clay, magnesium carbonate, calcium carbonate, aluminium oxide, aluminium hydroxide, silicon nitride, aluminium nitride Deng.It is small from specific gravity in these inorganic fillers, can with high proportion be compounded into composition, the aspect that low heat expansion is excellent set out, It is preferred that silica, wherein preferred spherical silicon dioxide.

In the hardening resin composition of the present application, the combination of fine cellulose fiber and silica is appropriate , in this case, the reduction effect of the linear expansion coefficient of solidfied material is more excellent, better with the adaptation of metallic conductor.

The average grain diameter of inorganic filler is preferably 3 μm or less, further preferred 1 μm or less.It should be noted that inorganic fill out The average grain diameter of material can be found out by laser diffraction formula particle size distribution analyzer.

For example, 25~90 mass %, it is preferably relative to the solid component of composition for the compounding amount of inorganic filler 30~90 mass %, more preferably 35~85 mass %.By the way that the compounding amount of inorganic filler is set as in above range, so as to The film performance of solidfied material after enough ensuring to solidify well.

Curing catalysts be mainly make heat-curing resin solidification person in curable resin, for example, can enumerate imidazoles, 2-methylimidazole, 2- ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2- phenylimidazole, 4- phenylimidazole, 1- cyano ethyl -2- benzene The imdazole derivatives such as base imidazoles, 1- (2- cyano ethyl) -2-ethyl-4-methylimidazole；Dicyandiamide, benzyldimethylamine, 2,4,4- (two Methylamino)-N, N- dimethyl benzyl amine, 4- methoxyl group-N, N- dimethyl benzyl amine, 4- methyl-N, N- dimethyl benzyl amine The hydrazine compounds such as equal amine compounds, adipic dihydrazide, sebacic dihydrazide；The phosphorus compounds such as triphenylphosphine, dimethylamino Pyridine etc..In addition, as commercially available product, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (four countries' chemical conversion can be enumerated Industrial Co., Ltd's system), U-CAT3503N, U-CAT3502T, DBU, DBN, U-CATSA102, U-CAT5002 (San-Apro Ltd. make) etc., it may be used alone or in combination two or more.In addition it is equally possible that using guanamines, acetylguanamine, benzene And guanamines, melamine, 2,4- diamino -6- methacryloxyethyl-s-triazine, 2- vinyl -2,4- diamino-are equal Triazine, 2- vinyl -4,6- diamino-s-triazine isocyanuric acid adduct, 2,4- diamino -6- methacryloxy second The Striazine derivatives such as base-s-triazine isocyanuric acid adduct.

As curing catalysts, it is generally desirable to basic catalyst.Especially desirable is imidazoles, by using imidazoles, So as to take into account the curability and stability of composition, heat resistance can be improved.For the content of curing catalysts, relative to 100 mass parts of heat-curing resin, more than for example, 0.01 mass parts and 20 below the mass, more than preferably 0.05 mass parts And 15 below the mass, more than more preferably 0.1 mass parts and 15 below the mass.

In hot curing resin composition of the invention, in addition to hydrophobization fine cellulose fiber, heat-curing resin, nothing It can be suitable for being compounded other usual compounding ingredients according to its purposes other than machine filler and curing catalysts.

As other usual compounding ingredients, for example, colorant, organic solvent, dispersing agent, defoaming agent stream can be enumerated Flat agent, thixotropic agent, coupling agent, fire retardant etc..

Public affairs shown in color index (color index) can be used as coloring pigment, dyestuff etc. for colorant Know usual substance.For example, can enumerate pigment blue (Pigment Blue) 15,15:1,15:2,15:3,15:4,15:6,16, 60, solvent blue (Solvent Blue) 35,63,68,70,83,87,94,97,122,136,67,70, naphthol green (Pigment Green) 7,36,3,5,20,28, solvent yellow (Solvent Yellow) 163, pigment yellow (Pigment Yellow) 24,108, 193、147、199、202、110、109、139、179、185、93、94、95、128、155、166、180、120、151、154、156、 175,181,1,2,3,4,5,6,9,10,12,61,62,62:1,65,73,74,75,97,100,104,105,111,116, 167、168、169、182、183、12、13、14、16、17、55、63、81、83、87、126、127、152、170、172、174、 176,188,198, pigment orange (Pigment Orange) 1,5,13,14,16,17,24,34,36,38,40,43,46,49,51, 61,63,64,71,73, paratonere (Pigment Red) 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31, 32、112、114、146、147、151、170、184、187、188、193、210、245、253、258、266、267、268、269、 37,38,41,48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,52:2,53:1,53:2,57:1,58:4,63: 1,63:2,64:1,68,171,175,176,185,208,123,149,166,178,179,190,194,224,254,255, 264,270,272,220,144,166,214,220,221,242,168,177,216,122,202,206,207,209, solvent Red (Solvent Red) 135,179,149,150,52,207, pigment violet (Pigment Violet) 19,23,29,32,36, 38,42, solvent violet (Solvent Violet) 13,36, pigment brown (Pigment Brown) 23,25, pigment black (Pigment Black) 1,7 etc..

The content of colorant is, for example, 0.01 mass % or more and 3 mass % in all compositions hereinafter, preferably 0.05 mass % or more and 1 mass % or less, more preferably 0.1 mass % or more and 0.5 mass % or less.In addition, using oxygen In the case where changing the cured film to obtain white such as titanium, be, for example, 1 mass % or more and 65 mass % in all compositions with Under, preferably 3 mass % or more and 60 mass % or less, more preferably 5 mass % or more and 50 mass % or less.

As organic solvent, the ketones such as methyl ethyl ketone, cyclohexanone can be enumerated；The aromatic series such as toluene, dimethylbenzene, durol Hydro carbons；Methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, diethyl The glycol ethers such as 2-ethoxyethanol, dipropylene glycol monoethyl ether, Triethylene glycol ethyl ether；Ethyl acetate, butyl acetate, cellosolve second The esters such as the carboxylate of acid esters, diethylene glycol monoethyl ether acetic acid esters and above-mentioned glycol ethers；Ethyl alcohol, propyl alcohol, ethylene glycol, propylene glycol Equal alcohols；The aliphatic hydrocarbons such as the amides such as dimethylformamide, dimethyl acetamide, octane, decane；Petroleum ether, naphtha, Petroleum series solvent such as hydrogenated naphtha, solvent naphtha etc..

As dispersing agent, polycarboxylic-acid, naphthalenesulfonic acid formalin condensation system, polyethylene glycol, polycarboxylic acids part can be used The high-molecular type dispersing agents such as Arrcostab system, polyether system, polyalkylene polyamine system, alkyl sulfonic acid system, quaternary ammonium system, higher alcohol alkylene oxide Low molecules type dispersing agents such as system, polyol ester system, alkyl polyamine system etc..

As defoaming agent levelling agent, can be used organosilicon, modified organic silicon, mineral oil, vegetable oil, aliphatic alcohol, Fatty acid, metallic soap, fatty acid amide, polyether polyols, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid esters etc. Compound etc..

As thixotropic agent, silica particle, silica dioxide gel, unsetting inorganic particle, polyamide-based can be used Additive, modified urea system additive, wax system additive etc..

As coupling agent, can be used as alkoxy is methoxyl group, ethyoxyl, acetyl group etc., as reactive functional Group is vinyl, methylacryloyl, acryloyl group, epoxy group, cyclic annular epoxy group, sulfydryl, amino, diamino, acid anhydrides, urea Base, thioether group (sulfide), isocyanates etc., for example, vinylethoxysilane, vinyltrimethoxysilane, ethylene The ethylene base system silanizations such as base three ('beta '-methoxy ethyoxyl) silane, γ-methacryloxypropyl trimethoxy silane Close object, gamma-amino propyl trimethoxy silicane, N- β-(amino-ethyl) gamma-amino propyl trimethoxy silicane, N- β-(amino Ethyl) the amino system silane compound such as gamma-amino hydroxypropyl methyl dimethoxysilane, γ-ureidopropyltriethoxysilane, γ-glycidoxypropyltrime,hoxysilane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane, the third oxygen of γ-epoxy The sulfydryls system such as epoxy silane compounds, the γ mercaptopropyitrimethoxy silanes such as base hydroxypropyl methyl diethoxy silane silane The silane coupling agents, isopropyl such as the phenylaminos base system silane compounds such as compound, N- phenyl-gamma-amino propyl trimethoxy silicane Three isostearoyl base titanate esters of base, four octyls bis- (two (tridecyl) phosphite esters) titanate esters, bis- (dioctylphyrophosphoric acids Ester) ethoxyacetic acid ester titanate esters, (dodecyl) benzenesulfonyl of isopropyl three titanate esters, isopropyl three (dioctylphyrophosphoric acid ester) Bis- (dioctyl phosphito ester) titanate esters of titanate esters, tetra isopropyl, four (1,1- diene propoxy methyl -1- butyl) double-(two (tridecyl)) phosphite ester titanate esters, bis- (dioctylphyrophosphoric acid ester) ethylene titanate esters, three caprylyl titanate esters of isopropyl, Isopropyl Dimethylacryloyl isostearoyl base titanate esters, three stearyl of isopropyl, two acryloyl group titanate esters, isopropyl It is three (dioctyl phosphate) titanate esters, three cumyl phenyl titanate esters of isopropyl, dicumylphenyl ethoxyacetic acid ester titanate esters, two different The titanate esters system such as stearyl ethylene titanate esters coupling agent, contains new alkoxy at the compound containing olefinic unsaturation zirconate It is the compound of zirconate, the new trineodecanoyl zirconate of new alkoxy three, (dodecyl) benzenesulfonyl of new alkoxy three zirconate, new (dioctyl) Zirconium phosphoester of alkoxy three acid esters, (dioctyl) pyrophosphate of new alkoxy three zirconate, three (ethylene of new alkoxy Diamino) ethyl zirconate, new alkoxy three (amino) phenyl zirconate, four (2,2- diene propoxy methyl) butyl, two (two (tridecyl)) phosphite ester zirconate, neopentyl (diallyl) oxygroup, three new trineodecanoyl zirconates, neopentyl (two Allyl) oxygroup, three (dodecyl) benzene-sulfonyl zirconate, neopentyl (diallyl) oxygroup, three (dioctyl) phosphates Zirconate, neopentyl (diallyl) oxygroup, three (dioctyl) pyrophosphate zirconates, neopentyl (diallyl) oxygroup, three (N- ethylene diamino) ethyl zirconate, neopentyl (diallyl) oxygroup, three (amino) phenyl zirconates, neopentyl (two Allyl) oxygroup, trimethacrylate acyl group zirconate, neopentyl (diallyl) oxygroup, triacryl zirconate, two new penta Base (diallyl) oxygroup, two p-benzoyl base zirconates, di neo-pentyl (diallyl) oxygroup, two (3- sulfydryl) propionic acid Bis- (2- propoxy methyl) butoxy (butanolato) of ester zirconate, zirconium (IV) 2,2-, [2,2- (the double 2- propoxyl group first of ring two Base) butoxy] the zirconates system coupling agent, diisobutyl (oil base) acetoacetyl aluminate, alkyl second such as pyrophosphate-O, O The Aluminates such as ethyl sodio acetoacetic ester aluminum-diisopropoxide system coupling agent etc..

Make fire retardant, the hydrated metals such as aluminium hydroxide, magnesium hydroxide system, red phosphorus, ammonium phosphate, ammonium carbonate, boron can be used Sour zinc, molybdenum compound system, bromine compounds system, chlorine compound system, phosphate, phosphorus-containing polyol, contains phosphamidon, melamine at zinc stannate Amine cyanurate, melamine compound, triaizine compounds, guanidine compound, silicon polymer etc..

(Photocurable resin composition)

Photocurable resin composition of the invention preferably comprises light-cured resin, inorganic filler, Photoepolymerizationinitiater initiater And colorant etc..

As light-cured resin, it is generally desirable to curing reaction can be carried out using active energy beam irradiation using having The resin of functional group can be free-radical polymerised or cationically polymerizable.

For example, compound, alicyclic ring epoxy compound, the oxygen in molecule with 1 or more ethylenic unsaturated bond can be enumerated Oxetane compounds are, it is preferable to use with the compound of 1 or more ethylenic unsaturated bond in molecule.

As the compound with ethylenic unsaturated bond, known usual optical polymerism oligomer and optical polymerism second are used Alkenyl monomer etc..

As above-mentioned optical polymerism oligomer, it is low that unsaturated polyester system oligomer, (methyl) acrylic ester can be enumerated Polymers etc..As (methyl) acrylic ester oligomer, phenol Novolac epoxy (methyl) acrylate, cresols can be enumerated Epoxies (methyl) acrylate, amino such as novolak type epoxy (methyl) acrylate, biphenol type epoxy (methyl) acrylate Formic acid esters (methyl) acrylate, epoxy amino formic acid esters (methyl) acrylate, polyester (methyl) acrylate, polyethers (first Base) acrylate, polybutadiene-modified (methyl) acrylate etc..

It should be noted that in this specification, (methyl) acrylate refer to by acrylate, methacrylate and it Mixture general name term, it is also the same about other similar statement.

As above-mentioned optical polymerism vinyl monomer, known usual vinyl monomer, such as styrene, chlorine can be enumerated The styrene derivatives such as styrene, α-methylstyrene；The vinyl such as vinyl acetate, vinyl butyrate or vinyl benzoate Esters；Vinyl isobutyl ether, vinyl n-butyl ether, vinyl tertbutyl ether, vinyl n-pentyl ether, vinyl isopentyl Ether, vinyl n-octadecane base ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ethers, triethylene glycol monomethyl ethylene The vinyl ethers such as base ether；Acrylamide, Methacrylamide, N- hydroxymethylacrylamide, N- hydroxymethyl metering system (methyl) third such as amide, N- methoxy acrylamide, N- ethoxymethyl acrylamide, N- butoxy methyl acrylamide Acrylamide；The allyls chemical combination such as Triallyl isocyanurate, diallyl phthalate, diallyl isophthalate Object；(methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) third The esters of (methyl) acrylic acid such as olefin(e) acid isobornyl thiocyanoacetate, (methyl) phenyl acrylate, (methyl) phenoxyethyl acrylate；(first Base) (methyl) acrylic acid such as Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, pentaerythrite three (methyl) acrylate Hydroxy alkyl esters；The alkoxyalkylenes such as methoxy ethyl (methyl) acrylate, ethoxyethyl group (methyl) acrylate Glycol list (methyl) esters of acrylic acid；Ethylene glycol two (methyl) acrylate, butanediol two (methyl) esters of acrylic acid, new penta 2 Alcohol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, season Poly- (methyl) acrylic acid of the alkylidene polyols such as penta tetrol four (methyl) acrylate, dipentaerythritol six (methyl) acrylate Ester；Diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, ethoxylated trimethylolpropane 3 third Poly- (methyl) acrylate of the polyether polyols such as olefin(e) acid ester, propoxylation trimethylolpropane tris (methyl) acrylate Class；Poly- (methyl) esters of acrylic acid such as 3-hydroxypivalic acid neopentyl glycol ester two (methyl) acrylate；Three [(methyl) acryloyl-oxies Base ethyl] poly- (methyl) esters of acrylic acid of isocyanurate types such as isocyanuric acid ester etc..

As alicyclic ring epoxy compound, bis- (3, the 4- epoxide rings of 3,4,3 ', 4 '-diepoxy bicyclohexane, 2,2- can be enumerated Hexyl) propane, bis- (3,4- the epoxycyclohexyl) -1,3- hexafluoropropane of 2,2-, bis- (3,4- epoxycyclohexyl) methane, 1- [1,1- Bis- (3,4- epoxycyclohexyls)] ethylo benzene, bis- (3,4- epoxycyclohexyl) adipate esters, 3,4- epoxycyclohexyl-methyl (3,4- Epoxy) cyclohexane carboxylate, (3,4- epoxy -6- methylcyclohexyl) methyl -3 ', 4 '-epoxy -6- methylcyclohexanecarboxylic acid esters, Bis- (the 3,4- 7-oxa-bicyclo[4.1.0 carboxylic acid) esters of ethylene -1,2-, cyclohexene oxide, 3,4- epoxycyclohexyl-methyl alcohol, 3,4- epoxide ring Hexyl ethyl trimethoxy silane etc. has the alicyclic ring epoxy compound etc. of epoxy group.

As commercially available product, for example, can enumerate the CELLOXIDE 2000 of DAICEL chemical industry Co. Ltd. system, CELLOXIDE 2021,CELLOXIDE 3000,EHPE3150；The EPOMIK VG-3101 of Mitsui Chemicals, Inc； The E-1031S of Yuka-Shell Epoxy Co.Ltd.；TETRAD-X, TETRAD- of Mitsubishi Gas Chemical Co., Ltd C；EPB-13, EPB-27 etc. of Tso Tat Co., Ltd., Japan.

As oxetane compound, in addition to bis- [(3- methyl -3- oxetanylmethoxy) methyl] ethers, double [(3- ethyl -3- oxetanylmethoxy) methyl] ether, bis- [(3- methyl -3- oxetanylmethoxy) first of 1,4- Base] benzene, bis- [(3- ethyl -3- oxetanylmethoxy) methyl] benzene of 1,4-, (3- methyl -3- oxetanyl) methyl Acrylate, (3- ethyl -3- oxetanyl) methacrylate, (3- methyl -3- oxetanyl) methyl Acrylate, (3- ethyl -3- oxetanyl) methylmethacylate, their oligomer or copolymer etc. are multifunctional Other than oxetanes class, oxetanes alcohol and novolac resin, poly- (4-Vinyl phenol), cardo can be also enumerated Type bisphenols, calixarene kind, cup resorcinol aromatic hydrocarbons or silsesquioxane etc. have the etherate of the resin of hydroxyl, have The oxetane compounds such as the copolymer of the unsaturated monomer of oxetanes ring and (methyl) alkyl acrylate.

As commercially available product, can enumerate ETERNACOLL OXBP of Ube Industries, Ltd, OXMA, OXBP, EHO, Xyxylene dioxygen azetidine, Toagosei Co., Ltd ARON OXETANE OXT-101, OXT-201, OXT- 211, OXT-221, OXT-212, OXT-610, PNOX-1009 etc..

Photoepolymerizationinitiater initiater is that can gather for making light-cured resin solidification person in curable resin for optical free radical Close initiator, or light cationic polymerization initiator.

As optical free radical polymerization initiator, for example, can enumerate benzoin, benzoin methyl ether, benzoin ethyl ether, The benzoins such as benzoin isopropyl ether and benzoin alkyl ethers；Acetophenone, 2,2- dimethoxy -2- phenyl acetophenone, 2,2- The acetophenones such as diethoxy -2- phenyl acetophenone, 2,2- diethoxy -2- phenyl acetophenone, 1,1- dichloroacetophenone；2- first Base -1- [4- (methyl thio) phenyl] -2- morpholinopropane -1- ketone, 2- benzyl -2- dimethylamino -1- (4- morpholinyl benzene Base)-butanone -1,2- (dimethylamino) -2- [(4- aminomethyl phenyl) methyl] -1- [4- (4- morpholinyl) phenyl] -1- butanone etc. Amino alkylphenone class；The Anthraquinones such as 2-methylanthraquinone, 2- ethyl hydrazine, 2- tert-butyl anthraquinone, 1- chloroanthraquinone；2,4- dimethyl The thioxanthene ketone class such as thioxanthones, 2,4- diethyl thioxanthone, 2-chlorothioxanthone, 2,4- diisopropylthioxanthone；Acetophenone dimethyl The ketals class such as ketal, benzil dimethyl ketal；The benzophenones such as benzophenone；Or xanthene ketone；(2,6- dimethoxy benzene Formoxyl) -2,4,4- amyl phosphine oxide, bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides, 2,4,6- trimethylbenzene first The phosphinoxides such as acyl group diphenyl phosphine oxide, ethyl -2,4,6- trimethylbenzoyl phenyl phosphate；Various peroxide Class, titanocenes series initiators etc..These can be with N, N- dimethyl amino benzoate, N, and N- dimethylaminobenzoic acid is different Photosensitizers of tertiary amines such as pentyl ester, amyl -4- dimethyl aminobenzoate, triethylamine, triethanolamine etc. are applied in combination.

As light cationic polymerization initiator, for example, diazonium salt, salt compounded of iodine, bromide, villaumite, sulfonium can be enumerated The salt such as salt, selenium salt, pyralium salt, thiapyran salt, pyridiniujm；Three (trihalomethyl group) s-triazine and its derivative etc. are halogenated Compound；The 2- nitrobenzyl ester of sulfonic acid；Iminosulfonate；1- oxo -2- azo naphthoquinones -4- sulfonate derivatives；N- hydroxyl Base acid imide=sulphonic acid ester；Three (methanesulfonyloxy group) benzene derivatives；Double sulfonyidiazomethanes classes；Sulfonyl carbonyl alkane Class；Sulfonyl carbonyl diazomethane class；Two sulphones etc..

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

For the compounding amount of Photoepolymerizationinitiater initiater, in terms of solid component conversion, relative to 100 mass of light-cured resin Part, for example, 0.05~20 mass parts, preferably 0.1~15 mass parts, more preferably 0.5~10 mass parts.By with the model Compounding Photoepolymerizationinitiater initiater is enclosed, so that the photo-curable on copper is abundant, the curability of film is good, and chemical resistance etc. applies Membrane property improves, in addition, deep curability also improves.

As inorganic filler, nothing same as inorganic filler used in above-mentioned hot curing resin composition can be used Machine filler, compounding amount also can be set to equally.

As colorant, it can be used and similarly coloured with colorant used in above-mentioned hot curing resin composition Agent.By the inclusion of colorant, even if so that the accumulated light of Photocurable resin composition irradiation surplus, can also prevent closely sealed The reduction of property.In addition, also can be improved the identification of film.

In Photocurable resin composition of the invention, in addition to hydrophobization fine cellulose fiber, light-cured resin, nothing It can also be suitable for being compounded other usual compounding ingredients according to its purposes other than machine filler, Photoepolymerizationinitiater initiater and colorant.

As other usual compounding ingredients, for example, organic solvent, dispersing agent, defoaming agent levelling agent, touching can be enumerated Become agent, coupling agent, fire retardant etc..As the organic solvent, dispersing agent, defoaming agent levelling agent, thixotropic agent, coupling agent, resistance Agent is fired, substance same as hot curing resin composition can be used.

(light solidifying/heat solidifying resin composition)

Light solidifying/heat solidifying resin composition of the invention includes light-cured resin and heat-curing resin, especially It is in the case that the developable using aqueous alkali is made in light solidifying/heat solidifying resin composition of the invention, preferably It is to contain carboxy resin as curable resin.

Containing carboxy resin can be used with 1 or more photosensitive unsaturated double-bond it is photosensitive containing carboxy resin, And contain any one of carboxy resin without photosensitive unsaturated double-bond, it is not particularly limited.It especially can be appropriate Ground uses the resin of act set forth below.

(1) contain carboxy resin and right by what the copolymerization of unsaturated carboxylic acid and compound with unsaturated double-bond obtained It is modified and have adjusted molecular weight, acid value containing carboxy resin.

(2) make that there is oxirane ring and olefinic insatiable hunger in carboxylic (methyl) acrylic copolymer resin and 1 molecule Photoresist containing carboxyl obtained from compound reaction with group.

(3) make compound and with unsaturated double-bondization that 1 epoxy group and unsaturated double-bond are respectively provided in 1 molecule The copolymer for closing object is reacted with unsaturated monocarboxylic, makes the secondary hydroxyl generated by the reaction and saturation or unsaturated multi-anhydride Photoresist containing carboxyl obtained from reaction.

(4) after reacting hydroxyl polymer-containing with saturated or unsaturated multi-anhydride, make the carboxylic generated by the reaction The sense of hydroxyl and carboxyl obtained from acid is reacted with the compound for being respectively provided with 1 epoxy group and unsaturated double-bond in 1 molecule Photosensitiveness resin.

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

(6) make multi-functional epoxy compound in, 1 molecule with 2 or more hydroxyls and with the hydroxyl of epoxy reaction with The compound of 1 outer reactive group is reacted with the monocarboxylic acid containing unsaturated group, the reaction product and multi-anhydride made Photoresist containing carboxyl obtained from reaction.

(7) it reacts the resin with phenolic hydroxyl group with the monocarboxylic acid containing unsaturated group with the reaction product of alkylene oxide, makes Photoresist containing carboxyl obtained from obtained reaction product is reacted with multi-anhydride.

(8) make multi-functional epoxy compound in, 1 molecule with the compound of at least one alcoholic extract hydroxyl group and 1 phenolic hydroxyl group Reacted with, the monocarboxylic acid containing unsaturated group, the alcoholic extract hydroxyl group of the reaction product made reacted with the anhydride group of multi-anhydride and Obtained photoresist containing carboxyl.

For light-cured resin used in light solidifying/heat solidifying resin composition of the invention and Thermocurable Substance same as above-mentioned light-cured resin and heat-curing resin can be used in resin.Photo-curable thermosetting of the invention The property changed resin combination preferably also includes above-mentioned inorganic filler, curing catalysts and Photoepolymerizationinitiater initiater, root than that described above It can be suitable for being compounded other usual compounding ingredients according to its purposes.

As other usual compounding ingredients, for example, above-mentioned colorant, organic solvent, dispersing agent, defoaming can be enumerated Agent levelling agent, thixotropic agent, coupling agent, fire retardant etc..

Hardening resin composition of the invention, which can carry out dry film, to be come using can also use in liquid form. It can may be 2 fluidities or more for 1 fluidity in liquid form in the case where use.As 2 fluidity compositions, for example, can Using the composition for having separated hydrophobization fine cellulose fiber and curable resin.

Then, dry film of the invention has by the way that hardening resin composition of the invention to be coated on carrier thin film simultaneously Resin layer obtained from drying.When forming dry film, firstly, hardening resin composition of the invention is dilute with above-mentioned organic solvent It releases and is adjusted to viscosity appropriate, utilize comma coater, knife type coater, lip type coating machine, bar coating machine, extrusion coated Machine, reverse coating machine, transfer roll-coater, gravure coater, Bracewell coater etc. are on carrier thin film with the painting of uniform thickness Cloth.Then, by coated composition usually in 40~130 DEG C of at a temperature of progress drying in 1~30 minute, it is possible thereby to be formed Resin layer.Coating film thickness is not particularly limited, in general, 3~150 μm are calculated as with the film thickness after drying, preferably at 5~60 μm Range is suitable for selection.

As carrier thin film, using plastic film, it is poly- that it is, for example, possible to use polyethylene terephthalates (PET) etc. Ester film, Kapton, polyamidoimide film, polypropylene film, polystyrene film etc..To the thickness of carrier thin film Degree is not particularly limited, in general, carrying out in the range of 10~150 μm is suitable for selection.More preferably 15~130 μm of range.

After forming the resin layer formed by hardening resin composition of the invention on carrier thin film, for preventing dust It is attached to the purpose on surface of resin layer etc., strippable covering film preferably and then on the surface of resin layer is laminated.As can The covering film of removing, it is, for example, possible to use polyethylene films, polytetrafluoroethylene film, polypropylene film, surface treated Paper etc..As covering film, will covering film removing when, bonding force between resin layer is less than resin layer and carrier thin film Bonding force.

It should be noted that hardening resin composition of the invention is coated on above-mentioned covering film in the present invention And it is dry, resin layer is consequently formed, carrier thin film can be laminated on its surface.That is, being coated with when as manufacture dry film in the present invention Any one in carrier thin film and covering film can be used in the film of hardening resin composition of the invention.

Printed circuit board of the invention has to be obtained by the resin layer of hardening resin composition or dry film of the invention Solidfied material.As the manufacturing method of printed circuit board of the invention, firstly, for example, using above-mentioned organic solvent, it will be of the invention Hardening resin composition is adjusted to the viscosity suitable for coating method, is coated with by Dipcoat method, flow coat method, rolling method, stick After the methods of method, silk screen print method, curtain coating processes are coated on substrate, 60~100 DEG C at a temperature of make institute in composition The organic solvent volatile dry (temporarily dry) contained, is consequently formed tack-free resin layer.In addition, being utilized in the case where dry film After laminating machine etc. fits in resin layer on substrate in a manner of contacting with substrate, carrier thin film is removed, thus the shape on substrate At resin layer.

As above-mentioned base material, other than being formed with the printed circuit board of circuit, flexible printed circuit board by copper etc. in advance, It can also enumerate and utilize paper phenol, paper epoxy resin, glass cloth epoxy resin, glass polyimides, glass cloth/non-woven fabrics asphalt mixtures modified by epoxy resin Rouge, glass cloth/paper epoxy resin, synthetic fibers epoxy resin, fluororesin polyethylene polyphenylene ether (polyphenylene oxide (Polyphenylene oxide)) cyanate etc. the materials, whole grades (FR-4 etc.) such as high-frequency circuit copper-clad laminated board Copper-clad laminated board and metal substrate, Kapton, PET film, polyethylene naphthalate (PEN) film, glass Glass substrate, ceramic substrate, wafer board etc..

For the volatile dry carried out after being coated with hardening resin composition of the invention, heated air circulation type can be used Drying oven, IR furnace, hot plate, convection oven etc. (using the heat source person for having the air heating method based on steam, make in drying machine Hot air convection contact method and in such a way that nozzle is blowed to supporter) Lai Jinhang.

Composition of the invention be hot curing resin composition in the case where, the coating composition on substrate and form painting Film, or dry film is laminated and after forming resin layer, for example, being heated to about 100~180 DEG C of temperature to make its thermosetting Change, thus, it is possible to form the cured film of each excellents such as heat resistance, chemical resistance, resistance to hygroscopicity, adaptation, electrical characteristics (solidfied material).

Composition of the invention be Photocurable resin composition in the case where, the coating composition on substrate and form painting Film, or dry film is laminated after forming resin layer, irradiation active energy beam is to form cured film (solidfied material).Separately Outside, as needed, film can be heated before the irradiation of active energy beam.

In the case that composition of the invention is the light solidifying/heat solidifying resin composition of alkali developable, in printing electricity After forming resin layer on the plate of road, the photomask by being formed with predetermined pattern is exposed optionally by active energy beam Unexposed portion is developed with dilute alkaline aqueous solution (for example, 0.3~3 mass % aqueous sodium carbonate), forms solidfied material by light Pattern.In turn, solidfied material is irradiated after active energy beam after being heating and curing (for example, 100~220 DEG C) or being heating and curing and is shone It penetrates active energy beam or only so that it is finally solidified (formal solidification) by being heating and curing, it is each that adaptation, hardness etc. is consequently formed The cured film of excellent.It should be noted that composition of the invention can be solid comprising above-mentioned heat-curing resin and light Change property resin and do not carry out development treatment non-developable light solidifying/heat solidifying resin composition.

As exposure machine used in the irradiation of above-mentioned active energy beam, as long as to be installed with high-pressure sodium lamp, ultra high pressure mercury Lamp, metal halide lamp, mercury short-arc lamp etc. simultaneously in turn can also with the device of the range illumination ultraviolet light of 350~450nm To use direct drawing apparatus (for example, describing the laser direct imaging of image according to the CAD data Direct Laser from computer Device).As the lamp source or laser light source for directly describing machine, maximum wavelength may be at the range of 350~450nm.For The light exposure that image is formed is different according to film thickness etc., is typically set to 10~1000mJ/cm², be preferably set to 20~800mJ/cm² In the range of.

As above-mentioned developing method, infusion process, spray process, spray-on process, spread coating etc. can use, it, can as developer solution To use the aqueous alkali of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium metasilicate, ammonia, amine etc..

Embodiment

Hereinafter, using embodiment, the present invention will be described in more detail.It should be noted that the compounding in table below Amount all indicates mass parts.

(preparation of oxidation paper pulp)

(oxidation paper pulp 1)

Use bleached kraft pulp (the FLETCHER CHALLENGE CANADA LTD system, trade name of coniferous tree " Machenzie ", CSF650ml) it is used as native cellulose fibre.As TEMPO, using commercially available product (ALDRICH corporation, Freeradical, 98 mass %).As sodium hypochlorite, use commercially available product (Wako Pure Chemicals Co., Ltd. system).As sodium bromide, It uses commercially available product (Wako Pure Chemicals Co., Ltd. system).

Firstly, after the BK bleached kraft pulp fibres 100g of coniferous tree is sufficiently stirred in the ion exchange water of 9900g, it is right Pulp quality 100g successively adds 1.25 mass % of TEMPO, 12.5 mass % of sodium bromide, 28.4 mass % of sodium hypochlorite.Make With the constant device of pH (pH-stat), 0.5M sodium hydroxide is added dropwise, pH is remained 10.5.After carrying out (20 DEG C) reactions in 120 minutes, The dropwise addition for stopping sodium hydroxide obtaining oxidation paper pulp.Using ion exchange water, obtained oxidation paper pulp is sufficiently cleaned, Then it is carried out dehydrating, obtains the oxidation paper pulp of solid component 30.4%.

(oxidation paper pulp 2)

The raw material used is changed to the bleached hardwood kraft pulp (CENIBRA society system) from You Jiali tree, removes this In addition, by using method same as oxidation paper pulp 1, the oxidation paper pulp of solid component 30.4% is obtained.

(preparations of fine cellulose fiber aqueous dispersions)

(preparation example 1)

1.18g is aoxidized paper pulp 1 and ion exchange water 34.8g to be carried out at 10 miniaturizations with high pressure homogenizer with 150MPa Reason, obtains fine cellulose fiber dispersion liquid containing carboxyl (5.0 mass % of solid component concentration).The fine cellulose fiber is put down Equal fibre diameter is 2.7nm, average fiber length 578nm, average aspect ratio 214, carboxyl-content 1.4mmol/g.

(preparation example 2)

105.3g oxidation paper pulp 1 is diluted with the ion exchange water of 1000g, concentrated hydrochloric acid 346g is added, is prepared into oxygen The dispersion liquid for changing pulp solids constituent concentration 2.34wt%, concentration of hydrochloric acid 2.5M makes it flow back 3 minutes.To obtained oxidation paper Slurry is sufficiently cleaned, and the sour water solution TEMPO oxidation paper pulp of solid component 41% is obtained.Then, will oxidation paper pulp 0.88g and from Sub- exchanged water 35.12g carries out 10 miniaturizations processing with high pressure homogenizer with 150MPa, obtains fine cellulose fiber containing carboxyl Dispersion liquid (5.0 mass % of solid component concentration).The avarage fiber diameter of the fine cellulose fiber is 2.9nm, average fiber Length is 491nm, average aspect ratio 169, carboxyl-content 1.4mmol/g.

(preparation example 3)

Return time is changed to 10 minutes, it is in addition to this, fine containing carboxyl by method same as preparation example 2 manufacture Cellulose fibre.The avarage fiber diameter of the fine cellulose fiber is 4.6nm, average fiber length 331nm, be averaged major diameter Than being 5.0 matter for the solid component concentration of 72, carboxyl-content 1.4mmol/g, the fine cellulose fiber dispersion liquid containing carboxyl Measure %.

(preparation example 4)

Using oxidation paper pulp 2, in addition to this, it is fine that fine cellulose containing carboxyl is manufactured by method same as preparation example 3 Dimension.The avarage fiber diameter of the fine cellulose fiber is 11.0nm, average fiber length 187nm, average aspect ratio 17, Carboxyl-content is 1.1mmol/g, the solid component concentration of the fine cellulose fiber dispersion liquid containing carboxyl is 5.0 mass %.

(preparation example 5)

Return time is changed to 60 minutes, it is in addition to this, fine containing carboxyl by method same as preparation example 4 manufacture Cellulose fibre.The avarage fiber diameter of the fine cellulose fiber is 19.4nm, average fiber length 174nm, averagely grows Diameter is than being 5.0 matter for the solid component concentration of 9, carboxyl-content 1.1mmol/g, the fine cellulose fiber dispersion liquid containing carboxyl Measure %.

(production of the fine cellulose fiber DMF dispersion liquid with modification group)

(CNF1)

Fine cellulose fiber 40g obtained in preparation example 1 is put into the beaker for having magnetic stirring apparatus, stirrer (5.0 mass % of solid component concentration).Then, with relative to fine cellulose fiber carboxyl 1mol, be equivalent to amino and be The amount of 1.2mol puts into aniline, 4- methyl morpholine 0.34g, the DMT-MM 1.98g as condensing agent, is dissolved in DMF 300g. React reaction solution 14 hours under room temperature (25 DEG C).It is filtered, is cleaned with ethyl alcohol after reaction, by DMT-MM salt Removal carries out cleaning with DMF and solvent is replaced, thus obtains aromatic hydrocarbyl by amido bond and be linked to fine cellulose fiber Made of fine cellulose fiber DMF dispersion liquid.The solid component concentration of obtained fine cellulose fiber DMF dispersion liquid is 2.2 mass %.

(CNF2)

As fine cellulose fiber, fine cellulose fiber obtained in preparation example 1 is replaced in preparation example 2 and is obtained Fine cellulose fiber operated in the same way in addition to this with CNF1, obtain fine cellulose fiber DMF dispersion liquid (solid at Divide 5.0 mass %).

(CNF3)

Fine cellulose fiber 35g obtained in preparation example 2 is put into the beaker for having magnetic stirring apparatus, stirrer (5 mass % of solid component concentration).Then, with relative to fine cellulose fiber carboxyl 1mol, be equivalent to amino 1mol's Amount investment tetrabutylammonium hydroxide, is dissolved with DMF 300g.React reaction solution 1 hour under room temperature (25 DEG C).Reaction terminates After be filtered, cleaned with DMF, thus obtain the fine cellulose fiber for being bonded with amine salt in fine cellulose fiber. The solid component concentration of obtained fine cellulose fiber DMF dispersion liquid is 4.0 mass %.

(CNF4)

As fine cellulose fiber, fine cellulose fiber obtained in preparation example 2 is replaced in preparation example 3 and is obtained Fine cellulose fiber, tetrabutylammonium hydroxide is replaced with into JEFFAMINEM-600 (HUNTSMAN corporation), except this with Outside, it is operated in the same way with CNF3, obtains fine cellulose fiber DMF dispersion liquid (8.0 mass % of solid component).

(CNF5)

As fine cellulose fiber, fine cellulose fiber obtained in preparation example 1 is replaced in preparation example 4 and is obtained Fine cellulose fiber operated in the same way in addition to this with CNF1, obtain fine cellulose fiber DMF dispersion liquid (solid at Divide 12.0 mass %).

(CNF6)

As fine cellulose fiber, fine cellulose fiber obtained in preparation example 1 is replaced in preparation example 5 and is obtained Fine cellulose fiber in addition to this, operated in the same way with CNF1 by aniline instead of octadecylamine, obtain fine fibre Cellulose fiber DMF dispersion liquid (13.0 mass % of solid component).

For these each fine cellulose fibers, it is shown in following tables 1 together.

[table 1]

(containing the preparation of carboxy resin used in hardening resin composition)

[synthesis example 1]

(varnish 1)

Add in 2 liters of removable flasks for having blender, thermometer, reflux condenser, dropping funel and nitrogen ingress pipe Enter the diethylene glycol dimethyl ether 900g as solvent and the tert-butyl hydroperoxide 2 ethyl hexanoic acid ester (day as polymerization initiator Oily Co. Ltd. system, trade name；Perbutyl O) 21.4g, it is heated to 90 DEG C.After heating, by methacrylic acid 309.9g, first Base methyl acrylate 116.4g and lactone-modified 2-hydroxyethyl methacrylate (Daicel Corporation. system, commodity Name；PLACCEL FM1) (day is oily with bis- (4- tert-butylcyclohexyl) peroxy dicarbonates as polymerization initiator by 109.8g Co. Ltd. system, trade name；PEROYL TCP) 21.4g together, be added thereto with 3 hours.In turn, make its curing 6 small When, thus obtain copolymer resins containing carboxyl.It should be noted that these reactions carry out in a nitrogen atmosphere.

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

[synthesis example 2]

(varnish 2)

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

By the resin solution it is cooling after, for it, use Tetrabutylammonium bromide as catalyst, 95~105 DEG C, it is 30 small When under conditions of, so that butyl glycidyl ether with the equivalent of 0.40 molar ratio and the carboxyl of obtained resin is carried out addition anti- It answers, it is cooling.

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

[synthesis example 3]

(varnish 3)

Cresol novolak type ring is added in the flask for having thermometer, blender, dropping funel and reflux condenser Oxygen resin (Dainippon Ink Chemicals's system, EPICLONN N-680, epoxide equivalent=210) 210g and the carbitol acetic acid as solvent Ester 96.4g makes its heating for dissolving.Then, it is added thereto as the quinhydrones 0.1g of polymerization inhibitor and as the three of catalysts Phenylphosphine 2.0g.The mixture is heated to 95~105 DEG C, acrylic acid 72g is slowly added dropwise, carries out reaction in about 16 hours until acid Value becomes 3.0mgKOH/g or less.After the reaction product is cooled to 80~90 DEG C, tetrabydrophthalic anhydride 76.1g is added, React within about 6 hours, until passing through infrared absorption analysis, the absorption peak (1780cm of acid anhydrides^-1) until disappearance.It is molten to the reaction The aromatic system solvent Ipsol#150 of 96.4g Idemitsu Kosen Co., Ltd. is added in liquid, is taken out after dilution.It obtains in this way The nonvolatile component of carboxylic photosensitive polymer solution is 65 mass %, the acid value of solid component is 78mgKOH/g.

(preparation of hardening resin composition)

It is equal using the mechanical industrial high pressure processed of Jitian after the compounding stirring of each ingredient according to the record in following tables 2~6 Matter machine Nanovater NVL-ES008, being repeated 6 times makes its dispersion, prepares each composition.It should be noted that in table 2~6 Numerical value indicates mass parts.

For the viscosity of each composition, with eastern machine industry flat plate-type viscometer TPE-100-H, using 1 ° 34 ' of plate, with Revolving speed 0.5rpm is measured.It the results are shown in table 2~6.It should be noted that being more than the determination limit of device, cannot surveying Fixed composition is denoted as cannot.

(hot curing resin composition)

It is coated with each composition with the applicator in 120 μm of gap in 38 μm of thickness of PET film, it is dry with heated air circulation type Furnace is 10 minutes dry at 90 DEG C, obtains the dry film with the resin layer of each composition.Then, with vacuum laminator in 60 DEG C, pressure 60 seconds copper foils for crimping and the resin layer of each composition being laminated to 18 μm of thickness are carried out under conditions of power 0.5MPa, by PET Film removing.Then being heated 30 minutes with heated air circulation type drying oven at 180 DEG C makes its solidification, and copper foil is removed, is solidified The sample of film.It should be noted that the viscosity of composition is high, cannot be denoted as with the composition that applicator is coated with cannot.

(Photocurable resin composition)

18 μm of copper foil of thickness is attached on the FR-4 copper-clad laminated board of thickness 1.6mm, with 120 μm of the applicator in gap It is coated with each composition, it is 10 minutes dry at 90 DEG C with heated air circulation type drying oven.Then, with the conveyor-type high pressure of 120W/cm Mercury lamp is with accumulated light 2000mJ/cm²It is irradiated.Then, copper foil is removed, obtains the sample of cured film.It needs to illustrate It is that the viscosity of composition is high, cannot be denoted as with the composition that applicator is coated with cannot.

(light solidifying/heat solidifying resin composition)

18 μm of copper foil of thickness is attached on the FR-4 copper-clad laminated board of thickness 1.6mm, with 120 μm of the applicator in gap It is coated with each composition, it is 10 minutes dry at 90 DEG C with heated air circulation type drying oven.Then, make with 3mm width × 30mm long The minus mask of pattern is closely sealed, with printed circuit board metal halide lamp exposure machine with 700mJ/cm²It is exposed.Then, Use 30 DEG C of 1wt%Na₂CO₃Developer solution, with developing machine carry out 60 seconds develop.Then, existed with heated air circulation type drying oven 150 DEG C of heating make its solidification in 60 minutes, and copper foil is removed, the sample of cured film is obtained.It should be noted that by the viscous of composition Degree is high, cannot be denoted as with the composition that applicator is coated with cannot.

(hot curing resin composition and Photocurable resin composition)

The thermal expansion measurement of production is cut into 3mm width × 30mm long with sample.To the test film, TA is used Instrument corporation TMA (Thermo mechanical Analysis) Q400, under stretch mode, 16mm between chuck, Heat up under load 30mN, nitrogen atmosphere, with 5 DEG C/min at 20~250 DEG C, then 250~20 DEG C with 5 DEG C/min into Row cooling is to measure.It finds out 30 DEG C~100 DEG C of average coefficient of thermal expansion α 1 when cooling and 200 DEG C~230 DEG C of evenly heat is swollen Swollen rate α 2.It the results are shown in table 2~6.

(light solidifying/heat solidifying resin composition)

Be used as received the sample of production, in addition to this, by with hot curing resin composition and light-cured resin The identical method of composition carries out.Show the result in table 2~6.

(hot curing resin composition)

In 38 μm of thickness of PET film, it is coated with each composition with 120 μm of the applicator in gap, it is dry with heated air circulation type Dry furnace is 10 minutes dry at 90 DEG C, obtains the dry film with the resin layer of each composition.Then, with vacuum laminator 60 DEG C, Crimping in 60 seconds is carried out under conditions of pressure 0.5MPa and the FR-4 that the resin layer of each composition is laminated to thickness 1.6mm is covered into copper Plywood removes PET film.Then being heated 30 minutes with heated air circulation type drying oven at 180 DEG C makes its solidification.Then, it presses (ATOTECH corporation), electroless copper (THRU-CUP PEA, C. Uyemura & Co Ltd's system), electro-coppering are decontaminated according to permanganic acid The sequence of processing is handled, and implements 25 μm of copper thickness of copper plating treatment on the resin layer.Then, heated air circulation type drying oven is used It carries out making annealing treatment for 60 minutes at 190 DEG C, obtains the test substrate for implementing copper plating treatment.It should be noted that composition Viscosity is high, cannot be denoted as with the composition that applicator is coated with cannot.

(Photocurable resin composition)

On the FR-4 copper-clad laminated board of thickness 1.6mm, it is coated with each composition with 120 μm of the applicator in gap, uses hot wind Circulating drying oven is 10 minutes dry at 90 DEG C.Then, with the conveyor-type high-pressure sodium lamp of 120W/cm with accumulated light 2000mJ/cm²Desciccator diaphragm is irradiated.Then, (ATOTECH corporation), electroless copper (THRU- are decontaminated according to permanganic acid CUP PEA, C. Uyemura & Co Ltd's system), plating Copper treatment sequence handled, in cured film implement 25 μm of copper thickness Copper plating treatment.Then, it is carried out making annealing treatment for 60 minutes at 190 DEG C with heated air circulation type drying oven, obtains implementing at copper facing The test substrate of reason.It should be noted that the viscosity of composition is high, cannot be denoted as with the composition that applicator is coated with cannot.

(light solidifying/heat solidifying resin composition)

On the FR-4 copper-clad laminated board of thickness 1.6mm, it is coated with each composition with 120 μm of the applicator in gap, uses hot wind Circulating drying oven is 10 minutes dry at 90 DEG C.Then, the mask for keeping whole face transparent is closely sealed, with printed circuit board metal halide Object lamp exposure machine is with 700mJ/cm²It is exposed.Then, using 30 DEG C of 1wt%Na₂CO₃Developer solution, carried out with developing machine Develop within 60 seconds.Then, being heated 60 minutes with heated air circulation type drying oven at 150 DEG C makes its solidification.Then it is removed according to permanganic acid Dirty (ATOTECH corporation), electroless copper (THRU-CUP PEA, C. Uyemura & Co Ltd's system), the sequence that Copper treatment is electroplated It is handled, implements 25 μm of copper thickness of copper plating treatment in cured film.Then, with heated air circulation type drying oven 190 DEG C into It makes annealing treatment within row 60 minutes, obtains the test substrate for implementing copper plating treatment.The viscosity of composition is high, cannot be coated with applicator Composition be denoted as cannot.

<copper-plated peel strength measurement>

The copper plating treatment sample of production is cut into 1cm width, length 7cm or more, uses Shimadzu Seisakusho Ltd.'s small desk Testing machine EZ-SX finds out the peel strength under 90 degree of angle using 90 ° of printing peel jigs.The results are shown in table 2~ 6。

(hot curing resin composition)

(process 1)

In 38 μm of thickness of PET film, it is coated with each composition with 120 μm of the applicator in gap, it is dry with heated air circulation type Dry furnace is 10 minutes dry at 90 DEG C, and production is formed with the film of the resin layer of each composition.It should be noted that composition is viscous Degree is high, cannot be denoted as with the composition that applicator is coated with cannot.

(process 2)

It completely eliminated the plate of copper foil by using the etching method of iron chloride in the FR-4 copper-clad laminated board to thickness 1.6mm It is with chemical resistance adhesive tape that 4 sides are slightly smaller than the 1st etching removal plate on (hreinafter referred to as " etching removal plate ") 4 sides of electrolytic copper foil of 18 μ m-thicks fix.In this state with the state for other than sticking portion being electrolytic copper foil exposing.It connects , chemical grinding is carried out to the electrolytic copper foil attached with MEC COMPANY LTD. EtchBond CZ-8101, production has The substrate of copper foil.

(process 3)

By the resin level of the film made in foregoing sequence 1, with vacuum laminator in 60 DEG C, the condition of pressure 0.5MPa Under be crimped on copper-clad surface 60 seconds of the substrate with copper foil made in foregoing sequence 2.Then PET film is removed.Then, Being heated with heated air circulation type drying oven at 180 DEG C makes its solidification for 30 minutes, and production is formed on the copper foil with the substrate of copper foil The test film of the cured film of each composition.

(process 4)

By 4 sides, the 2nd etching removal plate 2 fluidity epoxy bonding agent (Araldites slightly smaller than the copper foil of test film Standard it) is adhered to the solidification film surface of the test film made in process 3, places solidify 5 at 60 DEG C after sixty minutes at room temperature Hour.It is cut into the size for the 2nd etching removal plate being bonded after solidifying with cutter, is detached from from the 1st etching removal plate, overturning front And the back side, it is produced in the cured film for being adhered to each composition of the 2nd etching removal plate and is formed with the copper foil through chemical grinding Peel strength test sample.

(Photocurable resin composition)

(process 1)

It completely eliminated the plate of copper foil by using the etching method of iron chloride in the FR-4 copper-clad laminated board to thickness 1.6mm It is with chemical resistance adhesive tape that 4 sides are slightly smaller than the 1st etching removal plate on (hreinafter referred to as " etching removal plate ") 4 sides of electrolytic copper foil of 18 μ m-thicks fix.In this state with the state for other than sticking portion being electrolytic copper foil exposing.It connects , chemical grinding is carried out to the electrolytic copper foil attached with MEC COMPANY LTD. Etch Bond CZ-8101, production has The substrate of copper foil.

(process 2)

On the substrate with copper foil made in foregoing sequence 1, it is coated with each composition with 120 μm of the applicator in gap, It is 10 minutes dry at 90 DEG C with heated air circulation type drying oven.Then, with the conveyor-type high-pressure sodium lamp of 120W/cm with accumulated light 2000mJ/cm²It is irradiated, production is formed with the test film of the cured film of each composition on the copper foil with the substrate of copper foil. It should be noted that the viscosity of composition is high, cannot be denoted as with the composition that applicator is coated with cannot.

(process 3)

By 4 sides, the 2nd etching removal plate 2 fluidity epoxy bonding agent (Araldites slightly smaller than the copper foil of test film Standard it) is adhered to the solidification film surface of the test film made in foregoing sequence 2, is placed at room temperature solid at 60 DEG C after sixty minutes Change 5 hours.It is cut into the size for the 2nd etching removal plate being bonded after solidifying with cutter, is detached from from the 1st etching removal plate, overturning Front and back is produced in the cured film for being adhered to each composition of the 2nd etching removal plate and is formed with the copper through chemical grinding The peel strength test sample of foil.

(light solidifying/heat solidifying resin composition)

(process 1)

(process 2)

On the substrate with copper foil made in foregoing sequence 1, it is coated with each composition with 120 μm of the applicator in gap, It is 10 minutes dry at 90 DEG C with heated air circulation type drying oven.Then, the mask for keeping whole face transparent is closely sealed, with printed circuit board gold Belong to halide lamp exposure machine with 700mJ/cm²It is exposed.Then, using 30 DEG C of 1wt%Na₂CO₃Developer solution, with development Machine develop within 60 seconds.Then, being heated with heated air circulation type drying oven at 150 DEG C makes its solidification for 60 minutes, and production has copper The test film of the cured film of each composition is formed on the copper foil of the substrate of foil.It should be noted that the viscosity of composition is high, no Can be denoted as with the composition that applicator is coated with cannot.

(process 3)

The peel strength test sample of production is cut to 1cm width, length 7cm or more, uses Shimadzu Seisakusho Ltd.'s system Small desk testing machine EZ-SX finds out the peel strength under 90 degree of angle using 90 ° of printing peel jigs.Its result is shown In table 2~6.

The sample with chemical grinding processing copper foil of production is cut to 1cm width, length 7cm or more, in order to inhale Wet moisture removal, it is 60 minutes dry at 100 DEG C.By the sample after drying in reflow soldering (270 DEG C of highest) repeatedly into After row 3 times processing, visual confirmation chemical grinding handles the presence or absence of the removing of copper foil.It will be denoted as zero without removing person, removing person will be remembered For ×.It the results are shown in table 2~6.

[table 2]

Heat-curing resin 1:EPICLONN 830 (bisphenol f type epoxy resin) Dainippon Ink Chemicals system

Heat-curing resin 2:JER827 (bisphenol A type epoxy resin) Mitsubishi chemical Co., Ltd system

Heat-curing resin 3:EPPN-502H (triphenylmethane type epoxy resin) Nippon Kayaku K. K system (solid 60% cyclohexanone varnish of ingredient)

Heat-curing resin 4:FX-293 (fluorenes type phenoxy resin) Sumitomo Chemical Co, Nippon Steel system (solid component 30% cyclohexanone varnish)

Heat-curing resin 5:HF-1 (phenol resol resins) is bright and is melted into Co. Ltd. system (60% ring of solid component Hexanone varnish)

Curing catalysts 1:2E4MZ (2-ethyl-4-methylimidazole) Shikoku Chem system

Filler 1: silica, ADMAFINE SO-C2Admatechs Company Limited system

Filler 2: barium sulfate, B-30SAKAI CHEMICAL INDUSTRY CO., LTD. system

Organic solvent 1: dimethylformamide

Defoaming agent 1:BYK-Chemie Japan corporation BYK-352

[table 3]

Light-cured resin 1: bisphenol-a epoxy acrylate Mitsubishi chemical Co., Ltd system

Light-cured resin 2: trimethylolpropane trimethacrylate

Light-cured resin 3:KAYAMER PM2 (phosphoric acid hydrogen=bis- [2- (methacryloxy) ethyl ester]) Japan chemical drug Co. Ltd. system

Light-cured resin 4:LIGHT ESTER HO Kyoeisha Chemical Co., Ltd. system

Photoepolymerizationinitiater initiater 1:2- ethyl hydrazine

Colorant 1: phthalocyanine blue

[table 4]

Curing catalysts 2: Crushing of Ultrafine melamine Misao Kusano system

Curing catalysts 3: dicyandiamide

Photoepolymerizationinitiater initiater 2:Irgacure 907BASF Co. Ltd. system

Light-cured resin 5: dipentaerythritol tetraacrylate

Heat-curing resin 6:TEPIC-H (triglycidyl group isocyanuric acid ester) Misao Kusano's system

[table 5]

[table 6]

As set forth in more detail above, it is thus identified that by using comprising by avarage fiber diameter be 0.1nm or more and 200nm with Under, average fiber length 600nm or less, the draw ratio for the ratio between indicating avarage fiber diameter and average fiber length for 1 or more and The curability tree of hydrophobization fine cellulose fiber and curable resin that 200 fine cellulose fibers containing carboxyl below obtain Oil/fat composition can obtain low heat expansion, the solidfied material with the excellent adhesion of metallic conductor.

Claims

1. a kind of printed circuit board hardening resin composition, which is characterized in that the resin combination includes microfibre Cellulose fiber and curable resin, the fine cellulose fiber are that the carboxyl of the fine cellulose fiber with carboxyl utilizes amine At least any one in compound and quaternary ammonium compound is modified to come made of hydrophobization,

The fine cellulose fiber with carboxyl, avarage fiber diameter be 0.1nm or more and 200nm or less, average fibre Dimension length is 600nm or less and average aspect ratio is 1 or more and 200 or less.

2. printed circuit board hardening resin composition according to claim 1, wherein also include silica.

3. printed circuit board hardening resin composition according to claim 1 or 2 is comprising Thermocurable tree At least any one in rouge and light-cured resin is as the curable resin.

4. a kind of dry film, which is characterized in that have printed circuit board curability according to any one of claims 1 to 3 Resin combination is coated on film and resin layer made of drying.

5. a kind of solidfied material, which is characterized in that it is to solidify printed circuit board according to any one of claims 1 to 3 Property resin combination solidification made of, or made of the resin layer of dry film as claimed in claim 4 is solidified.

6. a kind of printed circuit board, which is characterized in that have solidfied material described in claim 5.