CN108693702A - Hardening resin composition, laminate structure, its solidfied material and electronic unit - Google Patents

Abstract

The present invention relates to hardening resin composition, laminate structure, its solidfied material and electronic units.It provides:Meet that the requirement performance of solder mask and coating both sides, heat resistance, low-repulsion be excellent in the case where not damaging developability, the small hardening resin composition of warpage after heating.Additionally, it is provided:Meet the excellent hardening resin composition of the requirement performance, developability (alkali solubility), heat resistance (resistance to soldering heat performance) of solder mask and coating both sides.A kind of hardening resin composition, contains:Alkali-soluble polyimide resin;Alkali-soluble resin other than the polyimide resin;With curability compound.

Description

Hardening resin composition, laminate structure, its solidfied material and electronic unit

Technical field

The present invention relates to the useful hardening resin compositions of the insulating film as electronic units such as flexible printed circuit boards (hereinafter, being also referred to simply as " composition "), laminate structure, its solidfied material and electronic unit.

Background technology

In recent years, due to smart mobile phone, tablet computer terminal it is universal caused by electronic equipment small-sized slimming and Need the small spatialization of the electronic units such as circuit board.Therefore, bend and the expansion of the purposes of the flexible printed circuit board that can store, For flexible printed circuit board, it is desirable that have the so far above high reliability.

In view of this, currently, insulating film as the insulating reliability for ensuring flexible printed circuit board, widely used There is following hybrid technique:It is used with the excellent polyimides of the mechanical properties such as heat resistance and bendability in bending part (bending section) and is The coating (referring for example to patent document 1,2) on basis, mounting portion (un-flexed portion) is middle to use electrical insulating property, resistance to soldering heat performance Etc. excellent and the photosensitive polymer combination of microfabrication can be carried out.

That is, the coating based on polyimides needs the processing carried out using Dies ' Blanking, therefore, be unsuitable for fine Wiring.Therefore, it is necessary to must be partially combined using can be processed using photoetching process in the chip mounting portion of fine wiring The photosensitive polymer combination (solder resist) of alkali developable.

Existing technical literature

Patent document

Patent document 1:Japanese Unexamined Patent Application 62-263692 bulletins

Patent document 2:Japanese Unexamined Patent Application 63-110224 bulletins

Invention content

Problems to be solved by the invention

In this way, in the manufacturing process of previous flexible printed circuit board, it has to using the technique and shape for fitting over layer At the hybrid technique of the technique of solder mask, there is the problem of cost-effectivenes and workability difference.

In view of this, so far, it has studied and the insulating film as solder mask or the insulating film as coating is used as flexibility The solder mask and coating of printed circuit board, but the requirement to the small spatialization of circuit board can fully meet solder mask and covering Functionization has not yet been reached in the material of the requirement performance of layer both sides.

In addition, requiring developability (alkali solubility), heat resistance (resistance to soldering heat performance), low rebound for solder mask, coating Property (rebound elasticity) excellent, the various characteristics such as warpage (warpage after solidification) is small after heating.However, in order to ensure heat resistance and changing Warpage properties after kind low-repulsion, heating and when using the big alkali soluble resins of molecular weight, leading to the problem of can not develop. In addition, imide series resin has heat resistance, there is that the warpage after solidification is big, although carbamate system resin is low Rebound and low warpage, but have the problem of poor heat resistance.Come accordingly, for the composition of the various resins proposed is used in the past It says, in the case where not damaging developability, cannot be satisfied heat resistance and low-repulsion is excellent, the warpage after heating is small such complete Portion requires.

Therefore, it is a primary object of the present invention to provide:Meet the requirement performance of solder mask and coating both sides, not Damage the hardening resin composition that heat resistance in the case of developability, low-repulsion be excellent, the warpage after heating is small.

In addition, other objects of the present invention are, provide:Suitable for the insulating film of flexible printed circuit board etc., particularly curved The hardening resin composition, laminate structure of formation process while folding part (bending section) and mounting portion (un-flexed portion), its The ministrys of electronics industry such as solidfied material and flexible printed circuit board with the solidfied material as protective layers such as such as coatings or solder mask Part.

The solution to the problem

The inventors of the present invention have made intensive studies in order to solve the above problems, as a result so far complete with content below The present invention constituted for purport.

That is, the hardening resin composition of the present invention is characterized in that, contain:Alkali-soluble polyimide resin;This is poly- Alkali-soluble resin other than imide resin;With curability compound.

In the hardening resin composition of the present invention, the preferred polyamides of alkali-soluble resin other than aforementioned polyimide resin Amine imide resin, foregoing polyamides imide resin preferably have structure and the following general formula (2) institute shown in the following general formula (1) The polyamide-imide resin for the structure shown.

(X₁It is derived from the residue of the aliphatic diamine (a) for the dimeric dibasic acid that carbon number is 24~48, X₂For the fragrance with carboxyl The residue of race's diamines (b), Y are each independently cyclohexane ring or aromatic rings.)

In addition, the hardening resin composition of the present invention preferably also contains core shell rubber particles.In turn, solidification of the invention Property resin combination in, aforementioned polyimide resin preferably have carboxyl, more preferably have carboxyl and phenolic hydroxyl group.

In turn in addition, in the hardening resin composition of the present invention, said curing property compound preferred epoxy.

In addition, the laminate structure of the present invention is characterized in that having:Resin layer (A);With sandwiched resin layer (A) layer The resin layer (B) being laminated on base material,

Aforementioned resin layer (B) is formed by above-mentioned hardening resin composition, and aforementioned resin layer (A) is by including alkali solubility tree Fat and the alkali developable resin combination of heat reactivity compound are formed.

In addition, the solidfied material of the present invention is characterized in that, by above-mentioned hardening resin composition or above-mentioned laminate structure It is formed.

In turn, electronic unit of the invention is characterized in that, has the insulating film formed by above-mentioned solidfied material.

Herein, the electronic unit as the present invention, for example, insulating film made of having as follows:In flexible printing The layer that above-mentioned laminate structure is formed on circuit board injects capable patterning by illumination, pattern is formed simultaneously with developer solution.Separately Outside, without using above-mentioned laminate structure, it is possible to have insulating film made of following:In flexible printed circuit board On sequentially form resin layer (A) and resin layer (B), later, capable patterning is injected by illumination, figure is formed simultaneously with developer solution Case.It should be noted that " pattern " refers to solidfied material, the i.e. insulating film of pattern-like in the present invention.

The effect of invention

According to the present invention it is possible to provide:Meet the requirement performance of solder mask and coating both sides, damage developability In the case of heat resistance, low-repulsion be excellent, the warpage after heating is small hardening resin composition.Furthermore, it is possible to realize:It is suitable for While the insulating film, particularly bending part (bending section) of the electronic units such as flexible printed circuit board are with mounting portion (un-flexed portion) The hardening resin composition of formation process, laminate structure, its solidfied material and with the solidfied material as such as coating or The electronic units such as the flexible printed circuit board of the protective films such as solder mask.

Description of the drawings

Fig. 1 is the manufacturing method for the flexible printed circuit board for schematically showing an example for indicating the electronic unit of the present invention Artwork.

Fig. 2 is the manufacturing method for the flexible printed circuit board for schematically showing an example for indicating the electronic unit of the present invention Another artwork.

Reference sign

1 flexible printed wiring base material

2 conductor circuits

3 resin layers

4 resin layers

5 masks

Specific implementation mode

Hereinafter, being described in detail to embodiments of the present invention.

(hardening resin composition)

The hardening resin composition of the present invention contains:Alkali-soluble polyimide resin;In addition to this alkali-soluble Resin;With curability compound.

It, can by the alkali-soluble resin and curability compound containing alkali-soluble polyimide resin, in addition to this To realize the hardening resin composition of the requirement performance for meeting solder mask and coating both sides, developability, excellent heat resistance.

(alkali-soluble polyimide resin)

As alkali-soluble polyimide resin, if the functional group containing one or more of phenolic hydroxyl group, carboxyl and It can be developed with aqueous slkali, so that it may to use known common substance.

By the polyimide resin, the characteristics such as resistance to bend(ing), heat resistance become better.

Such alkali-soluble polyimide resin for example,:Make carboxylic acid anhydride component and amine component and/or isocyanide Resin obtained from the reaction of acid esters ingredient.Herein, alkali solubility group is led by using the amine component with carboxyl, phenolic hydroxyl group Enter.In addition, imidizate can be carried out with hot-imide, can also be carried out with chemical imidization, but also can be by him Be applied in combination and implement.

As carboxylic acid anhydride component, tetracarboxylic anhydride, tricarboxylic acid anhydride etc. can be enumerated, but is not limited to these acid anhydrides, as long as being The compound with anhydride group and carboxyl reacted with amino, isocyanate group, can also just use comprising its derivative.Separately Outside, these carboxylic acid anhydride components can be used alone or be applied in combination.

As amine component, can use the polyamines such as diamines, the aliphatic poly ether amines such as aliphatic diamine, aromatic diamine, Diamines with carboxyl, the diamines etc. with phenolic hydroxyl group.As amine component, it is not limited to these amine, it is necessary to use and at least can Import phenolic hydroxyl group, a kind of functional group in carboxyl amine.In addition, these amine components can be used alone or be applied in combination.

As isocyanate prepolymer composition, aromatic diisocyanate and its isomers, polymer, aliphatic two can be used different The diisocyanate such as cyanate, ester ring type diisocyanates and its isomers, other common diisocyanates, but not It is defined in these isocyanates.In addition, these isocyanate prepolymer compositions can be used alone or be applied in combination.

In the synthesis of such alkali-soluble polyimide resin, it can use that known there are commonly solvents.As upper Organic solvent is stated, as long as not react with carboxyanhydrides, amine, isocyanates as raw material and these dissolution of raw material Just there is no problem for solvent, does not limit its structure especially.From the high aspect of the dissolubility of raw material, particularly preferred N, N- diformazans The aprotics such as base formamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), gamma-butyrolacton are molten Agent.

Alkali-soluble polyimide resin such for the above-described, from the alkali solubility (development for making polyimide resin Property), it is good with the harmony of other characteristics such as the mechanical property of the solidfied material of the resin combination comprising polyimide resin Viewpoint is set out, acid value (solid constituent acid value) preferably 20~200mgKOH/g, more suitably preferably 60~150mgKOH/g.Tool For body, by making the acid value be 20mgKOH/g or more, alkali solubility, i.e. developability become good, in turn, light irradiate after with The crosslink density of heat curable component is got higher, and can obtain sufficient development contrast.In addition, by making the acid value be 200mgKOH/g is hereinafter, the PEB after can especially inhibiting aftermentioned light to irradiate (bakes (POST EXPOSURE after exposure BAKE)) the so-called heat in technique hazes, and process allowance becomes larger.

In addition, if it is considered that developability and cured coating film characteristic, then the molecule of such alkali-soluble polyimide resin The matter average molecular weight Mw preferably 100000 or less of amount, more preferable 1000~100000, further preferred 2000~50000.This point When son amount is 100000 or less, the alkali solubility in unexposed portion increases, and developability improves.On the other hand, molecular weight is 1000 or more When, after exposing PEB techniques, sufficient resistance to developability and solidification physical property can be obtained in exposure portion.

(the alkali-soluble resin other than polyimide resin)

As above-mentioned alkali-soluble resin, as long as the functional group containing one or more of phenolic hydroxyl group, carboxyl and can be Development can use known common substance in aqueous slkali.It is, for example, possible to use used in previous solder mask, it is carboxylic Resin or carboxylic photoresist.

In particular, from the superior resin of the characteristics such as resistance to bend(ing), heat resistance is obtained in the case where not damaging developability From the perspective of composition, it can be suitble to use alkali-soluble polyamide-imide resin.

Made by combining such alkali-soluble polyamide-imide resin with aforementioned alkali-soluble polyimide resin With can be provided in that heat resistance, low-repulsion in the case of not damaging developability be excellent and sticking up for low dielectric, after heating Bent small hardening resin composition.

Herein, the compounding as the alkali-soluble polyamide-imide resin, with aforementioned alkali-soluble polyimide resin Ratio can be set as 98 in terms of quality ratio:2~50:50, it is preferably set to 90:10~50:50.

(alkali-soluble polyamide-imide resin)

In the hardening resin composition of the present invention, as alkali-soluble polyamide-imide resin, as long as containing phenol The functional group of one or more of hydroxyl, carboxyl and it can develop in aqueous slkali and can use known common substance.

Such alkali-soluble polyamide-imide resin is for example, following resin etc.:Make carboxylic acid anhydride component and amine After ingredient reaction obtains acid imide compound, so that gained acid imide compound is reacted with isocyanate prepolymer composition and obtain.Herein, alkali soluble Property group is imported by using the amine component with carboxyl, phenolic hydroxyl group.In addition, imidizate can with hot-imide into Row, can also be carried out, and they can also be applied in combination and implement with chemical imidization.

As carboxylic acid anhydride component, tetracarboxylic anhydride, tricarboxylic acid anhydride etc. can be enumerated, but is not limited to these acid anhydrides, as long as being The compound with anhydride group and carboxyl reacted with amino, isocyanate group can be used comprising its derivative.In addition, These carboxylic acid anhydride components can be used alone or be applied in combination.

As amine component, can use the polyamines such as diamines, the aliphatic poly ether amines such as aliphatic diamine, aromatic diamine, Diamines with carboxyl, the diamines etc. with phenolic hydroxyl group.As amine component, it is not limited to these amine, it is necessary to use and at least can Import phenolic hydroxyl group, a kind of functional group in carboxyl amine.In addition, these amine components can be used alone or be applied in combination.

As isocyanate prepolymer composition, aromatic diisocyanate and its isomers, polymer, aliphatic two can be used different The diisocyanate such as cyanate, ester ring type diisocyanates and its isomers, other common diisocyanates, but not It is defined in these isocyanates.In addition, these isocyanate prepolymer compositions can be used alone or be applied in combination.

Alkali-soluble polyamide-imide resin such for the above-described, from the alkali soluble for making polyamide-imide resin It is property (developability), equal with other characteristics such as the mechanical property of the solidfied material of the resin combination comprising polyamide-imide resin From the perspective of weighing apparatus property is good, acid value (solid constituent acid value) is preferably set to 30mgKOH/g or more, is more preferably set as 30mgKOH/g~150mgKOH/g, particularly preferably it is set as 50mgKOH/g~120mgKOH/g.Specifically, by making the acid value For 30mgKOH/g or more, alkali solubility, i.e. developability become good, in turn, the crosslink density with heat curable component after light irradiation It gets higher, sufficient development contrast can be obtained.In addition, by making the acid value for 150mgKOH/g hereinafter, can especially press down The so-called heat made in PEB (POST EXPOSURE BAKE) technique after aftermentioned light irradiation hazes, and process allowance becomes larger.

In addition, if it is considered that developability and cured coating film characteristic, then the molecular weight of alkali-soluble polyamide-imide resin Matter average molecular weight preferably 20000 or less, more preferable 1000~15000, further preferred 2000~10000.Molecular weight is When 20000 or less, the alkali solubility in unexposed portion increases, and developability improves.On the other hand, it when molecular weight is 1000 or more, is exposing After light PEB techniques, sufficient resistance to developability and solidification physical property can be obtained in exposure portion.

Especially in the present invention, from further increasing developability aspect, more preferably using with the following general formula (1) Shown in structure shown in structure and the following general formula (2) polyamide-imide resin.

Herein, X₁The aliphatic diamine (a) for being derived from the dimeric dibasic acid that carbon number is 24~48 (is also referred to as " two in this specification Aggressiveness diamines (a) ") residue.X₂(" carboxylic diamines is also referred to as in this specification for the aromatic diamine (b) with carboxyl (b) " residue).Y is each independently cyclohexane ring or aromatic rings.

By that comprising structure shown in structure shown in above-mentioned general formula (1) and above-mentioned general formula (2), can be formed even if making The excellent polyamides of the alkali solubility that can also be dissolved in the case of mild aqueous slkali as aqueous sodium carbonate with 1.0 mass % Amine imide resin.In addition, the solidfied material of the resin combination comprising above-mentioned polyamide-imide resin can have it is excellent Dielectric property.

Dimer diamine (a) can by by the carboxyl in the dimer of the aliphatic unsaturated carboxylic acid of carbon number 12~24 into Row reductive amination and obtain.That is, aliphatic diamine, that is, dimer diamine (a) from dimeric dibasic acid can for example obtain as follows: The unsaturated fatty acids such as oleic acid, linoleic acid are made to polymerize to form dimeric dibasic acid, after being restored, amination is to obtain.As in this way Aliphatic diamine, (the CRODA of diamines i.e. PRIAMINE1073,1074,1075 of the skeleton with carbon number 36 can be used for example JAPAN Co. Ltd. systems, trade name) etc. commercially available products.Dimer diamine (a) preferably originates from the dimerization that carbon number is 28~44 sometimes Acid, the dimeric dibasic acid for being more preferably sometimes 32~40 from carbon number.

As the concrete example of carboxylic diamines (b), 3,5- diaminobenzoic acids, 3,4- diaminobenzene first can be enumerated Acid, 5,5 '-di-2-ethylhexylphosphine oxides (ortho-aminobenzoic acid), benzidine -3,3 '-dicarboxylic acids etc..Carboxylic diamines (b) can be by a kind Compound is constituted, and can also be made of multiple compounds.From the viewpoint of raw material is acquired, carboxylic diamines (b) is preferred Contain 3,5- diaminobenzoic acids, 5,5 '-di-2-ethylhexylphosphine oxides (ortho-aminobenzoic acid).

Shown in the content of structure shown in general formula (1) in above-mentioned polyamide-imide resin, above-mentioned and above-mentioned general formula (2) The relationship of content of structure do not limit.From the alkali solubility for making polyamide-imide resin and comprising polyamidoimide tree From the perspective of the harmonies of other characteristics such as the mechanical property of the solidfied material of the resin combination of fat is good, dimer diamine (a) content (unit:Quality %) preferably 20~60 mass %, more preferable 30~50 mass %.In this specification, " dimer The content of diamines (a) " refers to the dimer diamine (a) of the positioning of one of raw material when as manufacture polyamide-imide resin Input amount relative to manufactured polyamide-imide resin quality ratio.Herein, " manufactured polyamidoimide The quality of resin " refers to being subtracted in imidizate from the input amount of whole raw materials for manufacturing polyamide-imide resin Water (the H of generation₂O carbon dioxide gas (the CO) and in amidation generated₂) theoretical amount obtained from be worth.

From the viewpoint of the alkali solubility for improving polyamide-imide resin, Y in above-mentioned general formula (1) and above-mentioned general formula (2) Shown in part preferably have cyclohexane ring.From the alkali solubility for making polyamide-imide resin and comprising polyamidoimide tree From the perspective of the harmonies of other characteristics such as the mechanical property of the solidfied material of the resin combination of fat is good, for above-mentioned Y institutes The relationship of the amount of aromatic rings and cyclohexane ring in the part shown, mole of the content of cyclohexane ring relative to the content of aromatic rings Than preferably 85/15~100/0, it is more preferable 90/10~99/1, further preferred by 90/10~98/2.

Above-mentioned polyamide-imide resin can also have part-structure shown in the following general formula (i).

Herein, X₃(in this specification also referred to as the diamines (f) in addition to dimer diamine (a) and carboxylic diamines (b) For " other diamines (f) ") residue, Y in the same manner as above-mentioned general formula (1) and above-mentioned general formula (2), be each independently aromatic rings or Cyclohexane ring.Other diamines (f) can be made of a kind of compound, can also be made of multiple compounds.

As the concrete example of other diamines (f), the bis- &#91 of 2,2- can be enumerated;4- (4- amino-benzene oxygens) Ben Ji ]It is propane, double [4- (3- amino-benzene oxygens) Ben Ji ]Sulfone, Shuan [4- (4- amino-benzene oxygens) Ben Ji ]The bis- &#91 of sulfone, 2,2-;4- (4- amino-benzene oxygens) benzene Ji ]Hexafluoropropane, Shuan [4- (4- amino-benzene oxygens) Ben Ji ]Methane, 4,4 '-bis- (4- amino-benzene oxygens) biphenyl, Shuan [4- (4- ammonia Phenoxyl) Ben Ji ]Ether, Shuan [4- (4- amino-benzene oxygens) Ben Ji ]Bis- (4- amino-benzene oxygens) benzene of ketone, 1,3-, the bis- (4- of 1,4- Amino-benzene oxygen) benzene, 2,2 '-dimethyl diphenyls -4,4 '-diamines, 2,2 '-bis- (trifluoromethyl) biphenyl -4,4 '-diamines, 2,6, 2 ', 6 '-tetramethyls -4,4 '-diamines, 5,5 '-dimethyl -2,2 '-sulfonyl-biphenyl -4,4 '-diamines, 3,3 '-dihydroxy connection Benzene -4,4 '-diamines, (4,4 '-diamino) diphenyl ether, (4,4 '-diamino) diphenyl sulfone, (4,4 '-diamino) hexichol first Ketone, (3,3 '-diamino) benzophenone, (4,4 '-diamino) diphenyl methane, (4,4 '-diamino) diphenyl ether, (3,3 '- Diamino) aromatic diamines such as diphenyl ether, hexamethylene diamine, eight methylene diamines, decamethylene diamine, ten can be enumerated Dimethylene diamines, 18 methylene diamines, 4,4 '-di-2-ethylhexylphosphine oxides (cyclo-hexylamine), isophorone diamine, 1,4- hexamethylenes two The aliphatic diamines such as amine, norbornene diamines.

Above-mentioned polyamide-imide resin can have structure shown in the following general formula (ii).

Herein, Z can be aliphatic group, or include aromatic group.In the case of for aliphatic group, Can also include the alcyls such as cyclohexane ring.Using aftermentioned manufacturing method, Z becomes the residue of diisocyanate cpd (e).

The manufacturing method of above-mentioned polyamide-imide resin does not limit, and known common method can be used sub- by acyl Amination Technique and amide imide chemical industry skill and manufacture.

In imidizate technique, make dimer diamine (a), carboxylic diamines (b) and selected from by hexamethylene -1,2,4- Tricarboxylic acids -1,2- acid anhydrides (c) are reacted with a kind or 2 kinds in the group of trimellitic anhydride (d) composition obtains acid imide compound.

For the input amount of dimer diamine (a), preferably the content of dimer diamine (a) is as 20~60 mass %'s Amount, the content of more preferable dimer diamine (a) become the amount of 30~50 mass %.The definition of the content of dimer diamine (a) is such as It is aforementioned.

As needed, other diamines (f) can also be used together with carboxylic diamines (b) with dimer diamine (a).

From the viewpoint of the alkali solubility for improving polyamide-imide resin, it is preferable to use hexamethylene in imidizate technique Alkane -1,2,4- tricarboxylic acids -1,2- acid anhydrides (c).The dosage of hexamethylene -1,2,4- tricarboxylic acids -1,2- acid anhydrides (c) is relative to trimellitic anhydride (d) molar ratio of dosage preferably 85/15~100/0, more preferable 90/10~99/1, further preferred 90/10~98/2.

Acid imide compound (A) and the diamine compound (B) that uses are (specifically, refer to dimer diamine (a) in order to obtain With carboxylic diamines (b) and other diamines (f) used as needed) amount and acid anhydrides (C) (specifically, referring to choosing Free hexamethylene -1,2,4- tricarboxylic acids -1,2- acid anhydrides (c) and trimellitic anhydride (d) composition group in a kind or 2 kinds) amount pass System does not limit.The dosage of preferred anhydrides (C) relative to the dosage of diamine compound (B) molar ratio become 2.0 or more and 2.4 amounts below, the more preferably molar ratio become 2.0 or more and 2.2 amounts below.

In amide imide chemical industry skill, makes diisocyanate cpd (e) and obtained by above-mentioned imidizate technique Acid imide compound (A) is reacted, and is obtained comprising the polyamide-imide resin with the substance of structure shown in the following general formula (3).

The specific type of diisocyanate cpd (e) does not limit.Diisocyanate cpd (e) can be by a kind Compound is constituted, and can also be made of multiple compounds.

As the concrete example of diisocyanate cpd (e), 4,4 '-methyl diphenylene diisocyanates, 2 can be enumerated, 4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s, naphthalene -1,5- diisocyanate, O-phthalic support diisocyanate, The aromatic diisocyanates such as xylylene diisocyanate, 2,4 tolylene diisoeyanate dimer;Two isocyanide of hexa-methylene Acid esters, trimethyl hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, isophorone diisocyanate, drop ice Aliphatic diisocyanates such as piece alkene diisocyanate etc..From the alkali solubility and polyamidoimide for making polyamide-imide resin From the perspective of the translucency of resin is good, diisocyanate cpd (e) preferably comprises aliphatic isocyanates, two isocyanides The more preferable aliphatic isocyanates of ester compound (e).

The dosage of diisocyanate cpd (e) in amide imide chemical industry skill does not limit.From to polyamide acyl Asia Polyimide resin assign appropriateness alkali solubility from the perspective of, the dosage of diisocyanate cpd (e) with relative to acyl in order to obtain Group with imine moiety (A) and the terms of mole ratios of the amount of diamine compound (B) that uses, be preferably set to 0.3 or more and 1.0 or less, More preferably it is set as 0.4 or more and 0.95 or less, is particularly preferably set as 0.50 or more and 0.90 or less.

The polyamide-imide resin so manufactured includes the substance with structure shown in the following general formula (3).

In above-mentioned general formula (3), X is each independently diamines residue (residue of diamine compound (B)), and Y is each independently For aromatic rings or cyclohexane ring, Z is the residue of diisocyanate cpd (e).N is natural number.

(curability compound)

The hardening resin composition of the present invention also contains curability compound.As curability compound, can use With can pass through heat, light carry out curing reaction functional group known in common compound.For example,:With ring-type (sulphur) ether etc. can carry out the Thermocurable compound of the functional group of curing reaction caused by heat, have ethylenical unsaturated double bonds Group etc. can carry out the photocurable compound of the functional group of curing reaction caused by light, wherein it is preferable to use Thermocurables Compound particularly preferably uses epoxy resin.

As the epoxy resin, bisphenol A type epoxy resin, brominated epoxy resin, nobolak type epoxy tree can be enumerated Fat, bisphenol f type epoxy resin, bisphenol-A epoxy resin, glycidyl amine type epoxy resin, hydantoins type asphalt mixtures modified by epoxy resin Fat, alicyclic epoxy resin, trihydroxy benzene methylmethane type epoxy resin, union II toluene phenolic or united phenol-type epoxy resin or it Mixture;Bisphenol-s epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, hetero ring type epoxy resin, biphenyl phenolic aldehyde are clear Paint shaped epoxy resin, the epoxy resin containing naphthalene, the epoxy resin etc. with bicyclopentadiene skeleton.

In particular, in the case of using Thermocurable compound, above-mentioned Thermocurable compound is preferably with itself and alkali solubility Resin (polyimide resin, polyamide-imide resin etc.) equivalent proportion (the alkali solubilities group such as carboxyl:The thermosettings such as epoxy group The property changed group) become 1:0.1~1:10 ratio compounding.By being set as such compounding ratio, developability becomes good, can be with It is readily formed fine pattern.Above-mentioned equivalent proportion more preferable 1:0.2~1:5.

(core shell rubber particles)

The hardening resin composition of the present invention preferably also contains core shell rubber particles.Thus, it is possible to provide developability, resistance to Hot insulating film purposes that is excellent, being suitable for the electronic units such as flexible printed circuit board, can for example meet solder mask and cover The hardening resin composition of the requirement performance of cap rock both sides.

The core shell rubber particles for constituting the hardening resin composition of the present invention have in the case where no adaptation reduces Improve the function of flexibility caused by core shell rubber particles.

Core shell rubber particles refer to being made of the stratum nucleare different from each other formed and 1 or more shell for covering it more The rubber material of layer structure.For core shell rubber particles, as be described hereinafter, by the excellent material of flexibility constitute stratum nucleare, to other at Point the excellent material of compatibility constitute shell, to reach low elastic modulus caused by the compounding of rubber constituent and point It dissipates property and becomes good.

According to the composition of the feature combination of the present invention of core shell rubber particles as compounding, following existing skill can be played The distinctive effect not having in art:Even if can provide in the state of having carried out the heat treatment such as Reflow Soldering, in excessive bending Also flawless generation etc. has the solidfied material of excellent flexibility in experiment.

As the constituent material of stratum nucleare, the material for having flexibility excellent is used.Specifically, silicon-type bullet can be enumerated Property body, butadiene-based elastomer, styrene series elastomer, acrylic elastomer, polyolefin elastomer, organosilicon/propylene Compound based elastomers of acids etc..

On the other hand, as the constituent material of shell, using there is the material excellent to the compatibility of other compositions.For example, In the case that hardening resin composition contains epoxy resin, it is preferable to use with by the excellent material of the compatibility to epoxy resin Expect the core shell rubber particles of the shell constituted.More preferable acrylic resin, epoxy resin.

From the viewpoint of storage stability, such core shell rubber particles preferably have solidification reactivity group, as It may be photo-curable reactive group that above-mentioned curability reactive group, which can be Thermocurable reactive group,.In addition, nucleocapsid rubber Glue particle can have curability reactive group of more than two kinds.

As Thermocurable reactive group, hydroxyl, carboxyl, isocyanate group, imino group, epoxy group, oxa- can be enumerated Cyclobutyl, sulfydryl, methoxy, methoxy ethyl, ethoxyl methyl, ethoxyethyl group, oxazolinyls etc..More preferable epoxy Base.

As photo-curable reactive group, vinyl, styryl, methacrylic acid group, acrylic etc. can be enumerated. Also become appropriate to be a large amount of reactivity in filer content, preferably methacrylic acid group, acrylic.

Herein, it as the method for importing curability reactive group to the surface of core shell rubber particles, is not particularly limited, it can To use known common method.For example, when forming shell around stratum nucleare, as the constituent material of shell, will have with Material polymerization for the curability reactive group different from the stratum nucleare progress functional group of polymerisation is led in stratum nucleare Enter.

As the commercially available product of core shell rubber particles, Rohm&amp can be enumerated;Haas corporations ParaloidELX2655, Japan Synthetic rubber Co. Ltd. system XER-91 etc..

In the hardening resin composition of the present invention, from resistance to anti-thread breakage excellent aspect, core shell rubber particles are put down Equal grain size is preferably 2 μm or less.More preferably 0.01~1 μm.It should be noted that in this specification, average grain diameter refers to making With the value for the D50 that Nikkiso Company Limited's Microtrac Particle Size Analyzers measure.

In the hardening resin composition of the present invention, the content of core shell rubber particles is relative to the solid constituent in composition In organic principle be preferably 1~30 mass %.For 1 mass % or more when, be excellent from resistance to anti-thread breakage excellent aspect Choosing.On the other hand, be 30 mass % or less when, be preferred from the aspect that printing and developability are excellent.More preferably 3 ~20 mass %.In addition, the hardening resin composition of the present invention can contain the core shell rubbers with curability reactive group Particle and core shell rubber particles without curability reactive group.It should be noted that organic principle refers to herein, filler is removed Etc. solid whole components other than inorganic constituents.

(Photoepolymerizationinitiater initiater)

In the case that the hardening resin composition of the present invention forms photosensitive polymer combination, preferably also contain photopolymerization Initiator.As the Photoepolymerizationinitiater initiater, known common substance can be used, in particular, by the curable resin of the present invention In the case that composition is for the PEB techniques after the irradiation of aftermentioned light, being suitble to use also has the function as Photobase generator Photoepolymerizationinitiater initiater.It should be noted that in the PEB techniques, Photoepolymerizationinitiater initiater and Photobase generator can also be applied in combination.

Also it is following compound to have the Photoepolymerizationinitiater initiater of the function as Photobase generator:Pass through ultraviolet light, visible light Deng light irradiation and molecule structure change or molecular cleavage can be used as curability compound i.e. Thermocurable compound to generate Polymerisation the compound of a kind or more of alkaline matter that functions of catalyst.As alkaline matter, such as can lift Go out secondary amine, tertiary amine.

As such Photoepolymerizationinitiater initiater also with the function as Photobase generator, for example, alpha-amido benzene Ethanone compounds, have acyloxy imino group, N- formylated aromatic series amino, N- acylated aromatics race amino, nitre at oxime ester compound The compound etc. of the substituent groups such as base Benzylcarbamate base, alkoxybenzyl carbamate groups.Wherein, preferred oxime ester compound Object, alpha-aminoacetophenone compound, more preferable oxime ester compound.As alpha-aminoacetophenone compound, particularly preferably there are 2 The above nitrogen-atoms.

As long as intramolecular causes to split when having benzoin ehter bond in alpha-aminoacetophenone compound molecule, being irradiated by light Solution and the alkaline matter (amine) for generating performance solidification catalytic action.

As oxime ester compound, can be used as long as the compound to generate alkaline matter by light irradiation.

Such Photoepolymerizationinitiater initiater can be used alone, and can also combine two or more use.In resin combination Photoepolymerizationinitiater initiater compounding amount relative to 100 mass parts of total amount of alkali-soluble resin, preferably 0.1~40 mass parts, into One step preferably 0.3~15 mass parts.In the case of more than 0.1 mass parts, illumination part/non-irradiation unit can be obtained well The contrast of resistance to developability.In addition, in the case that 40 is below mass part, solidfied material characteristic improves.

It can further be compounded ingredient below as needed in the hardening resin composition of the present invention.

(macromolecule resin)

In order to improve flexibility, the dry to touch of gained solidfied material, hardening resin composition of the invention can be compounded Known common macromolecule resin.As such macromolecule resin, cellulose-based, Polyester, phenoxy resin can be enumerated Based polymer, polyvinyl acetal system, polyvinyl butyral system, polyamide-based, polyamidoimide system binder polymerization Object, elastomer etc..Such macromolecule resin can be used singly or in combination of two or more.

(inorganic filler)

In order to inhibit the cure shrinkage of solidfied material, improve the characteristics such as adaptation, hardness, curable resin of the invention combination Object can be compounded inorganic filler.As such inorganic filler, for example, barium sulfate, amorphous silica, Fused silica, spherical silicon dioxide, talcum, clay, magnesium carbonate, calcium carbonate, aluminium oxide, aluminium hydroxide, silicon nitride, nitridation Aluminium, boron nitride, nooy fort tripoli etc..

(colorant)

The present invention hardening resin composition can be compounded it is red, orange, blue, green, yellow, white, black etc. known in commonly colour Agent.Can be pigment, dyestuff, pigment as such colorant,.

(organic solvent)

In order to prepare resin combination, for the viscosity adjustment for being coated on base material, in carrier film, solidification of the invention Property resin combination can be compounded organic solvent.As such organic solvent, ketone, aromatic hydrocarbon, glycol can be enumerated Ethers, glycol ethers acetate esters, esters, alcohols, aliphatic hydrocarbon, oil series solvent etc..Such organic solvent can individually make With a kind, can also be used in the form of mixture of more than two kinds.

(other compositions)

The present invention hardening resin composition can further be compounded as needed sulfhydryl compound, closely sealed accelerating agent, The ingredients such as thermal curing catalyst, antioxidant, ultra-violet absorber.They can use known common substance.

Furthermore it is possible to be compounded common thickener known in fine particle silica, hydrotalcite, organobentonite, montmorillonite etc., It is known common as the antifoaming agent such as silicon-type, fluorine system, macromolecular and/or levelling agent, silane coupling agent, antirust agent etc. Additive kind.

Including such composition described above the present invention hardening resin composition can be suitable for being formed it is aftermentioned , there is resin layer (A) and sandwiched resin layer (A) to be laminated in the laminate structure of resin layer (B) of flexible printed circuit board , resin layer (B).

(laminate structure)

There is the laminate structure of the present invention resin layer (A) and sandwiched resin layer (A) to be laminated in flexible printed circuit board etc. Resin layer (B) on base material.

Herein, in laminate structure of the invention, resin layer (A) and resin layer (B) respectively essentially as adhesive linkage and Protective layer functions.The laminate structure of the present invention has feature at following aspect:Resin layer (B) is by above-mentioned curable resin Composition is formed, and resin layer (A) is by including the alkali developable resin combination of alkali soluble resins and heat reactivity compound It is formed.

In the present invention, by making the resin layer (B) of the upper layer side in the laminate structure that 2 layers of resin layer are laminated serve as reasons The hardening resin composition of aforementioned present invention is formed, excellent heat-resisting so as to be realized in the case where not damaging developability Property.In addition, by using polyamide-imide resin as the alkali-soluble resin other than polyimide resin, so as to Have excellent heat resistance, low-repulsion in the case of not damaging developability, and the warpage after heating can be reduced.In turn, By containing core shell rubber particles in the hardening resin composition of aforementioned present invention, so as to obtain having excellent show Flexibility after shadow, heat resistance and especially soft solder Reflow Soldering also excellent laminate structure.Under in laminate structure When containing core shell rubber particles in the resin layer (A) of layer side, there is the worry that adaptation reduces, by the resin layer for making upper layer side (B) it is formed by the above-mentioned hardening resin composition containing core shell rubber particles, thus can in the case where no adaptation reduces To obtain flexibility improvement effect caused by core shell rubber particles.As a result, in the present invention, core is free of in preferred resin layer (A) Shell rubber grain.

[Resin layer (A)s ]

(alkali developable resin combination)

As the alkali developable resin combination for constituting resin layer (A), as long as can be anti-comprising alkali soluble resins and heat The resin combination to develop in the aqueous slkali of answering property compound.As alkali soluble resins, can preferably enumerate:Including with The resin combination of the compound of phenolic hydroxyl group, the compound with carboxyl, the compound with phenolic hydroxyl group and carboxyl, can be with Use known common substance.

For example,:It is previous it is being used as solder mask composition, include carboxylic resin or carboxylic sense The resin combination of photosensitiveness resin, the compound with ethylenic unsaturated bond and heat reactivity compound.

Herein, as carboxylic resin or carboxylic photoresist and with the compound of ethylenic unsaturated bond, Known common compound can be used, in addition, as heat reactivity compound, can use has the energy such as cyclic annular (sulphur) ether Carry out the known common compound of the functional group of curing reaction caused by heat.

Such resin layer (A) can include Photoepolymerizationinitiater initiater can not also include Photoepolymerizationinitiater initiater, as comprising The Photoepolymerizationinitiater initiater used in the case of Photoepolymerizationinitiater initiater can be enumerated and be used in above-mentioned hardening resin composition The same substance of Photoepolymerizationinitiater initiater.

In resin layer (A), can contain in addition macromolecule resin, inorganic filler, colorant, organic solvent etc. with it is above-mentioned The same other compositions of hardening resin composition.

[Resin layer (B)s ]

Resin layer (B) is by alkali-soluble resin above-mentioned, containing alkali-soluble polyimide resin, in addition to this and admittedly The hardening resin composition of the property changed compound is formed, and for aspect in addition to this, is not particularly limited.

Herein, as above-mentioned alkali-soluble polyimide resin, alkali-soluble resin in addition to this, curability compound Deng can use and the same resin of the substance of hardening resin composition and compound etc. that constitute the present invention.

In addition, the above-mentioned hardening resin composition for constituting resin layer (B) includes:It is preferred that the alkali other than polyimide resin The resin of dissolubility, more preferable polyamide-imide resin further preferably have structure shown in aforementioned formula (1) and aforementioned logical The polyamide-imide resin of structure shown in formula (2).It, can be the case where not damaging developability by being constituted as formation Under obtain the superior resin combination of the characteristics such as resistance to bend(ing), heat resistance.

The present invention laminate structure due to bendability it is excellent, can be used for the ministrys of electronics industry such as flexible printed circuit board At least either in the bending section of part and un-flexed portion, for example, coating, solder mask that can be as flexible printed circuit board It is used at least wantonly a kind of purposes in interlayer dielectic.

Preferably as it, at least single side is supported the laminate structure of such present invention constituted described above with film Or the dry film of protection uses.

(dry film)

Dry film can for example manufacture as described below.

That is, first, the hardening resin composition of above-mentioned resin layer (B) will be constituted and constitute the alkali development of resin layer (A) Type resin combination is adjusted to viscosity appropriate with organic solvent diluting respectively, conventionally, with comma coater etc. Well known method is coated on successively in carrier film (support film).Later, usually 1~30 point is carried out with 50~130 DEG C of temperature Clock is dried, so as to make the dry film for the film for being formed with resin layer (B) and resin layer (A) in carrier film.For preventing Film coated surface adheres to the purpose of dust, and the cover film (protective film) that can be removed can further be laminated on the dry film.As load Body film and cover film, can be preferably small when that will cover film stripping for cover film suitable for using known plastic film In the film of resin layer and the bonding force of carrier film.For the thickness of carrier film and cover film, be not particularly limited, generally 10~ Suitable for selection in the range of 150 μm.

(solidfied material)

The solidfied material of the present invention is the hardening resin composition for making the aforementioned present invention or the stepped construction of the aforementioned present invention Obtained from body solidification.

(electronic unit)

The hardening resin composition and laminate structure of such present invention described above can be for example efficiently used for The electronic units such as flexible printed circuit board.Specifically, the flexible printing electricity of the solidfied material with following insulating film can be enumerated Road plate etc.:The hardening resin composition of the present invention, the layer of laminate structure are formed on flexible printed wiring base material, pass through light Irradiation is patterned, and forming pattern with developer solution forms.

Hereinafter, the manufacturing method of flexible printed circuit board is specifically described in an example as electronic unit.

(manufacturing method of flexible printed circuit board)

It for example can be according to the artwork institute of Fig. 1 using the manufacture of the flexible printed circuit board of the laminate structure of the present invention The step of showing and carry out.That is, being the manufacturing method for including following process:In the flexible printed wiring base material for being formed with conductor circuit The technique (lamination process) of the layer of the upper laminate structure for forming the present invention;The layer irradiation active-energy of the laminate structure is penetrated Line becomes the technique (exposure technology) of pattern-like;With the layer of the laminate structure is subjected to alkali development, forms patterned stacking The technique (developing process) of the layer of structure.In addition, as needed, further photocuring, heat can be carried out after alkaline development Cure (rear curing process), so that the layer of laminate structure is fully cured, obtain the high flexible printed circuit board of reliability.

In addition, the manufacture using the flexible printed circuit board of the laminate structure of the present invention for example can be according to the work of Fig. 2 Step shown in skill figure and carry out.That is, being the manufacturing method for including following process:In the flexible printing cloth for being formed with conductor circuit The technique (lamination process) of the layer of the laminate structure of the present invention is formed on line base material;Activity is irradiated to the layer of the laminate structure Energy-ray becomes the technique (exposure technology) of pattern-like;Technique (the heating (PEB) that the layer of the laminate structure is heated Technique);With the layer of laminate structure is subjected to alkali development, forms technique (the development work of the layer of patterned laminate structure Skill).In addition, as needed, can carrying out further photocuring, heat cure (rear curing process) after alkaline development, making stacking The layer of structure is fully cured, and obtains the high flexible printed circuit board of reliability.

Hereinafter, for each technique in Fig. 1 or Fig. 2, further it is described in detail.

[Ceng Diegongyi ]

In the technique, on being formed with the flexible printed wiring base material 1 of conductor circuit 2, formed by including alkali soluble resins Deng alkali developable resin combination resin layer 3 (resin layer (A)) and resin layer 3 on, curable resin group of the invention Close the laminate structure that the resin layer 4 (resin layer (B)) of object is formed.Herein, each resin layer for constituting laminate structure for example may be used With by the way that the resin combination for being constituted resin layer 3,4 is coated on wiring substrate 1 and dry to form resin layer 3,4 successively, Or the film layer by the way that the resin combination for constituting resin layer 3,4 to be made to the form of the dry film of 2 layers of structure is pressed on wiring substrate 1 Method and formed.

Resin combination to the coating method of wiring substrate can be knife type coater, lip coating machine, comma coater, Method well known to film coater etc..In addition, drying means can be to use heated air circulation type drying oven, IR stoves, hot plate, convection current Baking oven etc. has the device of the heat source of the mode of heating using steam, makes the method for the hot wind counter current contacting in drying machine;With, from Method well known to method that nozzle blows supporter etc..

[Bao Guanggongyi ]

In the technique, by irradiating active energy beam, to make contained in resin layer 4 Photoepolymerizationinitiater initiater activation at The pattern-like of minus, exposure portion is cured.In the case of composition using aftermentioned PEB techniques, makes to have and produce alkali as light Photoepolymerizationinitiater initiater or the Photobase generator activation of the function of agent make alkali generate at the pattern-like of minus.

As the exposure machine used in the technique, direct imaging apparatus, the exposure machine equipped with metal halide lamp can be used Deng.The mask of the exposure of pattern-like is the mask of minus.

As the active energy beam used in exposure, it is preferable to use maximum wavelength is in swashing for the range of 350~450nm Light beam or scattering light.By making maximum wavelength be the range, Photoepolymerizationinitiater initiater can be made to activate well with efficiency.In addition, its Light exposure is different according to film thickness etc., such as can be set as 50~1500mJ/cm²。

[PEB Gong Yis ]

In the technique, after exposure, resin layer is heated, to make exposure portion cure.By the technique, by using The composition of Photoepolymerizationinitiater initiater with the function as Photobase generator is formed by resin layer (B) or light has been applied in combination The composition of polymerization initiator and Photobase generator is formed by the alkali generated in the exposure technology of resin layer (B), can make resin Layer (B) is cured to deep.Heating temperature is, for example, 70~150 DEG C.Heating time is, for example, 1~120 minute.Tree in the present invention The ring-opening reaction of epoxy resin, therefore, solid in being reacted with optical free radical caused by the solidification of oil/fat composition for example, thermal response Change the case where carrying out to compare, strain, cure shrinkage can be inhibited.

[Xian Yinggongyi ]

In the technique, by alkali development, unexposed portion is removed, the insulating film of the pattern-like of minus is formed, for example covers Layer and solder mask.As developing method, method well known to impregnating can be based on.In addition, as developer solution, carbonic acid can be used The bucks such as the imidazoles such as sodium, potassium carbonate, potassium hydroxide, amine, 2-methylimidazole, tetramethyl ammonium hydroxide aqueous solution (TMAH) are molten Liquid or their mixed liquor.

[Gu Huagongyi &#93 afterwards;

It should be noted that after developing process, can light irradiation further be carried out to insulating film, in addition, for example also may be used To be heated with 150 DEG C or more.

Embodiment

Hereinafter, the present invention is further described in detail according to embodiment, comparative example, but the present invention is not implemented by these The limitation of example, comparative example.

(synthesis example 1)

In four mouthfuls of 300mL flasks for having nitrogen ingress pipe, thermometer, blender, input is used as two at room temperature Aliphatic diamine (CRODAJAPAN Co. Ltd. systems, the product name of the dimeric dibasic acid from carbon number 36 of aggressiveness diamines (a) PRIAMINE1075) 28.61g (0.052mol), the 3,5- diaminobenzoic acids 4.26g as carboxylic diamines (b) (0.028mol), gamma-butyrolacton 85.8g simultaneously dissolve.

Then, hexamethylene -1,2,4- tricarboxylic acid anhydrides (c) 30.12g (0.152mol), trimellitic anhydride (d) 3.07g are put into (0.016mol) is kept for 30 minutes at room temperature.Toluene 30g is further put into, 160 DEG C is warming up to, will be given birth to together with toluene At water removal after, keep 3 hours, be cooled to room temperature, to obtain the solution containing acid imide compound.

Trimethyl six methylene of the input as diisocyanate cpd (e) in gained is containing the solution of acid imide compound Group diisocyanate 14.30g (0.068mol) is kept for 32 hours at a temperature of 160 DEG C, is diluted with cyclohexanone 21.4g, to Obtain the solution (A-1) containing polyamide-imide resin.The matter average molecular weight Mw of gained polyamide-imide resin be 5250, Solid constituent is 41.5 mass %, the content of acid value 63mgKOH/g, dimer diamine (a) is 40.0 mass %.

(synthesis example 2)

In four mouthfuls of 300mL flasks for having nitrogen ingress pipe, thermometer, blender, input is used as two at room temperature Aliphatic diamine (CRODAJAPAN Co. Ltd. systems, the product name of the dimeric dibasic acid from carbon number 36 of aggressiveness diamines (a) PRIAMINE1075) 29.49g (0.054mol), the 3,5- diaminobenzoic acids 4.02g as carboxylic diamines (b) (0.026mol), gamma-butyrolacton 73.5g simultaneously dissolve.

Then, hexamethylene -1,2,4- tricarboxylic acid anhydrides (c) 31.71g (0.160mol), trimellitic anhydride (d) 1.54g are put into (0.008mol) is kept for 30 minutes at room temperature.Toluene 30g is further put into, 160 DEG C is warming up to, will be given birth to together with toluene At water removal after, keep 3 hours, be cooled to room temperature, to obtain the solution containing acid imide compound.

It is sub- as the trimethyl six of diisocyanate cpd (e) containing in the solution of acid imide compound, putting into gained Methyl diisocyanate 6.90g (0.033mol) and dicyclohexyl methyl hydride diisocyanate 8.61g (0.033mol), at 160 DEG C At a temperature of kept for 32 hours, with cyclohexanone 36.8g dilute, to obtain the solution (A-2) containing polyamide-imide resin. The matter average molecular weight Mw of gained polyamide-imide resin is 5840, solid constituent is 40.4 mass %, acid value 62mgKOH/ G, the content of dimer diamine (a) is 40.1 mass %.

(synthesis example 3)

In four mouthfuls of 300mL flasks for having nitrogen ingress pipe, thermometer, blender, it is bis- that 2,2 '-are put at room temperature [4- (4- amino-benzene oxygens) Ben Ji ]Propane 6.98g, 3,5- diaminobenzoic acid 3.80g, polyether diamine (Huntsman companies System, product name Elastamine RT1000, molecular weight 1025.64) it 8.21g and gamma-butyrolacton 86.49g and dissolves.

Then, hexamethylene -1,2 is put into, 4- tricarboxylic acids -1,2- acid anhydride 17.84g and trimellitic anhydride 2.88g are protected at room temperature It holds 30 minutes.Toluene 30g is further put into, is warming up to 160 DEG C, after removing the water generated together with toluene, holding 3 is small When, it is cooled to room temperature, to obtain acid imide compound solution.

Trimellitic anhydride 9.61g and trimethyl hexamethylene diisocyanate are put into gained acid imide compound solution 17.45g is kept for 32 hours at a temperature of 160 DEG C.In this way, obtaining the polyamideimide resin solution (A- containing carboxyl 3).Solid constituent is 40.1 mass %, acid value 83mgKOH/g.

(synthesis example 4)

In the removable three-necked flask for being equipped with blender, nitrogen ingress pipe, fractionating column, cooling tube, 3,3 '-diaminos are added Base -4,4 '-dihydroxy-diphenyl sulfone 22.4g, 2,2 '-bis- [4- (4- amino-benzene oxygens) Ben Ji ]Propane 8.2g, NMP 30g, γ- Butyrolactone 30g, 4, the double phthalic anhydride 27.9g of 4 '-oxygen, trimellitic anhydride 3.8g, in a nitrogen atmosphere, room temperature, with 100rpm is stirred 4 hours.Then, toluene 20g is added, while toluene and water distillation are removed flash trimming with 180 DEG C of silicon bath temperature, 150rpm Stirring 4 hours, obtains the polyimide resin solution (PI-1) with phenolic hydroxyl group and carboxyl.

The acid value of gained resin (solid constituent) is 18mgKOH, Mw 10000, hydroxyl equivalent 390.

(embodiment 1-1~1-9 and comparative example 1-1,1-2)

According to recorded in table 1 at being grouped as, by the material described in embodiment 1-1~1-9 and comparative example 1-1,1-2 point It is not compounded, after being pre-mixed with blender, is kneaded with triple-roller mill, prepare each resin combination for being used to form resin layer.In table Value is the mass parts of solid constituent unless otherwise specified.

[Table 1]

* 1-1) solution (A-1)~(A-3) containing polyamide-imide resin:1~synthesis example of synthesis example 3

* 1-2) alkali soluble resins (PI-1):Synthesis example 4

* 1-3) Photoepolymerizationinitiater initiater:Oxime system Photoepolymerizationinitiater initiater IRGACURE OXE02 (BASF Co. Ltd. systems)

* 1-4) epoxy resin:Bisphenol A type epoxy resin E828, epoxide equivalent 190,380 (Mitsubishi Chemical of matter average molecular weight Co. Ltd. system)

The formation > of < resin layers

Preparing thick 18 μm of the formation of copper has the flexible printed wiring base material of circuit, uses MEC COMPANY LTD.CZ- 8100 carry out pre-treatment.Later, by each resin combination obtained in embodiment 1-1~1-9 and comparative example 1-1,1-2 with respectively Film thickness after drying is coated on as 30 μm of mode on the flexible printed wiring base material for having carried out pre-treatment.Later, hot wind is used Circulating drying oven carries out drying in 30 minutes with 90 DEG C, forms uncured resin layer.

< developability (alkali solubility) >

For the above-mentioned uncured resin layer being formed with like that on each flexible printed wiring base material of resin layer, first, Using the exposure device (HMW-680-GW20) equipped with metal halide lamp, across negative mask, with 300mJ/cm², with formed The mode for the opening that 200 μm of diameter carries out pattern exposure.Substrate with the resin layer after exposure is carried out 30 minutes with 90 DEG C Heat treatment.Later, substrate is impregnated in the aqueous sodium carbonate of 30 DEG C of 1 mass % and develop within 1 minute, observe pattern The state of formation, evaluation developability (alkali solubility).Evaluation criteria is for example following.

○:Exposure portion shows that resistance to developability, unexposed portion show that developability, pattern are formed well.

×:Unexposed portion shows developability, but resolution ratio pattern is formed bad (resolution ratio is insufficient).

< heat resistances (resistance to soldering heat performance) >

(making of evaluation substrate)

For the above-mentioned uncured resin layer being formed with like that on each flexible printed wiring base material of resin layer, first, Using the exposure device (HMW-680-GW20) equipped with metal halide lamp, across negative mask, with 300mJ/cm², with formed The mode for the opening that 200 μm of diameter carries out pattern exposure.Later, after carrying out 30 minutes PEB techniques with 90 DEG C, developed (30 DEG C, 0.2MPa, 1 mass %Na₂CO₃Aqueous solution) 60 seconds, heat cure in 150 DEG C × 60 minutes is carried out, solidification is formed with to make Resin layer flexible printing wiring substrate (evaluation substrate).

(evaluation method)

For the above-mentioned evaluation substrate made like that, it is coated with rosin series scaling powder, is being redefined for 260 DEG C of soft solder It is impregnated in slot 20 seconds (10 seconds × 2 times), heat resistance (resistance to soldering heat is evaluated in the swelling stripping of observation cured coating film (resin layer) Performance).Evaluation criteria is for example following.

○:10 seconds × 2 times also no swelling strippings of dipping.

×:Swelling stripping is produced when impregnating 10 seconds × 1 time.

< chemical resistances (resistance to gold-plated property) >

Substrate is similarly evaluated using the evaluation with aforementioned heat resistance, is evaluated with the following method.

For evaluating substrate, bathed using the electroless nickel bath and chemical gilding of commercially available product, with 80~90 DEG C, 5 μm of nickel of implementation, The plating of 0.05 μm of gold observes substrate and resin layer, evaluation chemical resistance (resistance to gold-plated property).Evaluation criteria is for example following.

○:The case where between substrate and film (resin layer) without infiltration.

△:The case where infiltration being confirmed between substrate and film (resin layer).

×:The case where stripping being produced in a part for film (resin layer).

< resiliences (rebound elasticity) >

(making of test film)

Each resin combination obtained in embodiment 1-1~1-9 and comparative example 1-1,1-2 is distinguished with the film thickness after drying Mode as 30 μm is coated on Kapton, and drying in 30 minutes, shape are carried out with heated air circulation type drying oven, with 90 DEG C At uncured resin layer.Later, using the exposure device (HMW-680-GW20) equipped with metal halide lamp, not across covering Mould and with 300mJ/cm²It is exposed.After later, carrying out 30 minutes PEB techniques with 90 DEG C, developed (30 DEG C, 0.2MPa, 1 mass %Na₂CO₃Aqueous solution) 60 seconds, carried out heat cure with 150 DEG C × 60 minutes, to make be formed with it is cured The Kapton test film of resin layer.

(evaluation method)

The above-mentioned Kapton test film made like that is cut into 2cm × 7cm, so that the both ends of long side is overlapped, makes It becomes band-like circle, and electronic balance is fixed in the overlapping portion at both ends with adhesive tape.In the state that circle has been bent, with the upper of circle Under interval as the mode of 3mm, press trim ring with glass plate, measure load at this time and be used as screen resilience (g), evaluation resilience (rebound elasticity).Evaluation criteria is for example following.

○:Less than 30g.

△:30g is less than 45g.

×:45g or more.

Amount of warpage > after < solidifications

Using with the same test film of aforementioned elastic evaluation, evaluated with the following method.

After test film is cut into 5cm × 5cm, substrate is rested on to horizontal testing stand in such a way that warped surface becomes upper On, the distance at 4 positions in vertex is measured with ruler up to 1mm units, using the maximum value at 4 positions as sticking up respectively from testing stand Qu Liang, the amount of warpage after evaluation solidification.Evaluation criteria is for example following.

○:Amount of warpage is less than 3mm.

△:Amount of warpage 3mm is less than 6mm.

×:Amount of warpage 6mm or more

By these evaluation result is shown in table 2.

&#91;Table 2&#93;

(embodiment 1-10~1-12)

According to, at being grouped as, the material described in embodiment 1-10~1-12 being compounded respectively, with stirring described in table 3 It after machine premixing, is kneaded with triple-roller mill, prepares each resin combination for being used to form resin layer (A) and is used to form resin layer (B) each resin combination.Value in table is the mass parts of solid constituent unless otherwise specified.

&#91;Table 3&#93;

* 1-1) solution (A-1)~(A-3) containing polyamide-imide resin:1~synthesis example of synthesis example 3

* 1-2) alkali soluble resins (PI-1):Synthesis example 4

* 1-3) Photoepolymerizationinitiater initiater:Oxime system Photoepolymerizationinitiater initiater IRGACURE OXE02 (BASF Co. Ltd. systems)

* 1-4) epoxy resin:Bisphenol A type epoxy resin E828, epoxide equivalent 190,380 (Mitsubishi Chemical of matter average molecular weight Co. Ltd. system)

* 1-5) alkali soluble resins:P7-532:Urethane acrylate, acid value 47mgKOH/g (common prosperity society chemistry strain formula meetings Society's system)

* 1-6) photo-curable monomer:BPE-500:The Ethoxylated bisphenol A dimethylacrylates (villages Xin Zhong chemistry strain formula Commercial firm's system)

The formation > of < resin layers (A)

Preparing thick 18 μm of the formation of copper has the flexible printed wiring base material of circuit, uses MEC COMPANY LTD.CZ- 8100 carry out pre-treatment.Later, each resin combination of the resin layer (A) obtained in embodiment 1-10~1-12 will be used to form It is coated on the flexible printed wiring base material for having carried out pre-treatment in such a way that the film thickness after drying respectively becomes 20 μm.Later, Drying in 30 minutes is carried out with heated air circulation type drying oven, with 90 DEG C, forms resin layer.

The formation > of < resin layers (B)

Each resin combination of the resin layer (B) obtained in embodiment 1-10~1-12 will be used to form with the film after drying The mode that thickness respectively becomes 10 μm is coated on the resin layer (A) formed among the above.Later, with heated air circulation type drying oven, with 90 DEG C of progress drying in 30 minutes, forms resin layer (B).

It is formed as the resin layer (A) and resin described in embodiment 1-10~1-12 so on flexible printed wiring base material The uncured laminate structure that layer (B) is formed.

For the above-mentioned uncured laminate structure formed like that, implement to be directed to embodiment 1-1 using same method The evaluation that uncured resin layer in~1-9 and comparative example 1-1,1-2 carries out.

By these evaluation result is shown in table 4.

&#91;Table 4&#93;

The evaluation result shown in table 2 and 4 clearly confirms, in the resin combination of each embodiment, can obtain excellent Low warpage properties after developability, heat resistance, low-repulsion and heating.

(embodiment 2-1~2-5 and comparative example 2-1,2-2)

According to described in table 5 at being grouped as, by the material described in embodiment 2-1~2-5 and comparative example 2-1,2-2 point It is not compounded, after being pre-mixed with blender, is kneaded with triple-roller mill, prepare the resin combination for being used to form each resin layer.In table Value is the mass parts of solid constituent unless otherwise specified.

&#91;Table 5&#93;

* 2-1) alkali soluble resins 1 (PI-1):Synthesis example 4

* 2-2) alkali soluble resins 2:Carboxylic epoxy acrylate ZAR-1035 (acid value 98mgKOH/g, Japanese chemical drug Co. Ltd. system)

* 2-3) solution (A-1) containing polyamidoimide:Synthesis example 1

* 2-4) oxime system Photoepolymerizationinitiater initiater:IRGACURE OXE02 (BASF Co. Ltd. systems)

* 2-5) epoxy resin:Bisphenol A type epoxy resin E828, epoxide equivalent 190,380 (Mitsubishi Chemical of matter average molecular weight Co. Ltd. system)

* 2-6) core-shell polymer 1:Paraloid EXL-2655(Rohm&Haas corporations)

* 2-7) core-shell polymer 2:Staphyloid AC-3355 (GANZ is melted into Co., Ltd.)

* 2-8) masterbatch 1 that is formed by core-shell polymer:(" Araldite (registered trademark) " MY721:75 mass %/core Core-shell polymeric particles A (volume average particle sizes:100nm, core part:Butadiene/Styrene Gong Jujuhewu &#91;Tg:-25℃&#93;, shell Part:Methyl methacrylate/glycidyl methacrylate/styrene copolymerized polymer):The masterbatch of 25 mass %), it needs It is synthesized it is noted that core/shell polymer particles A is the method recorded by Japanese Unexamined Patent Publication 2005-248109 bulletins.Wherein, The ratio of Butadiene/Styrene is set as 50 mass of mass %/50 %.In addition, after manufacture Afpol latex, To add first relative to the ratio that 100 mass % of the Afpol latex is 5 mass of mass %/5 mass of %/5 % Base methyl acrylate/glycidyl methacrylate/styrene, is graft-polymerized.

* 2-9) acrylate:The Ethoxylated bisphenol A dimethylacrylates BPE-900 (villages Xin Zhong chemistry strain formulas Commercial firm's system)

The formation > of < resin layers (A)

Preparing thick 18 μm of the formation of copper has the flexible printed wiring base material of circuit, uses the CZ- of MEC COMPANY LTD. 8100 carry out pre-treatment.Later, each resin layer (A) obtained in embodiment 2-1~2-4 and comparative example 2-1,2-2 will be constituted Resin combination is coated on the flexible printed wiring base for having carried out pre-treatment in such a way that the film thickness after drying respectively becomes 25 μm On material.Later, it is dried with heated air circulation type drying oven, with 90 DEG C/30 minutes, forms resin layer (A).

The formation > of < resin layers (B)

By the resin combination for constituting each resin layer (B) obtained in embodiment 2-1~2-4 and comparative example 2-1,2-2 with The mode that film thickness after drying respectively becomes 10 μm is coated on the resin layer (A) formed among the above.Later, heated air circulation type is used Drying oven was dried with 90 DEG C/30 minutes, formed resin layer (B).

It is formed as the tree described in embodiment 2-1~2-4 and comparative example 2-1,2-2 so on flexible printed wiring base material The uncured layer lamination structural body that lipid layer (A) and resin layer (B) are formed.

< developability (alkali solubility) >

For such as above-mentioned uncured laminate structure being formed on each flexible printed wiring base material of laminate structure, First, using the exposure device (HMW-680-GW20) equipped with metal halide lamp, across negative mask, with 500mJ/cm², with The mode for forming the opening of 200 μm of diameter carries out pattern exposure.By the substrate with the uncured layer lamination structural body after exposure with 90 DEG C heat within 30 minutes.Later, substrate is impregnated in 30 DEG C of the aqueous sodium carbonate of 1 mass %, carries out 1 point Clock develops, and what evaluation 200 μm of patterns of opening were formed could.Evaluation criteria is for example following.

○:Exposure portion shows that resistance to developability, unexposed portion show that developability, pattern are formed well.

△:Unexposed portion shows developability, but the resistance to developability of exposure portion is insufficient, can not carry out pattern and be formed.

×:Unexposed portion is not dissolved in developer solution, therefore can not carry out pattern and be formed.

< heat resistances >

For such as above-mentioned uncured laminate structure being formed on each flexible printed wiring base material of laminate structure, First, using the exposure device (HMW-680-GW20) equipped with metal halide lamp, across negative mask, with 500mJ/cm², with The mode for forming the opening of 200 μm of diameter carries out pattern exposure.Later, after carrying out 30 minutes PEB techniques with 90 DEG C, develop (30 DEG C, 0.2MPa, 1 mass %Na₂CO₃Aqueous solution) 60 seconds, carry out heat cure in 150 DEG C × 60 minutes, to make be formed with through Cross the flexible printing wiring substrate (evaluation substrate) of cured laminate structure.It is coated with rosin series on the evaluation substrate and helps weldering Agent impregnates 20 seconds (10 seconds × 2 times) in the soft solder slot for being redefined for 260 DEG C, and the swelling of cured coating film is removed It is evaluated.Evaluation criteria is for example following.

○:Without swelling stripping impregnating 10 seconds × 2 times.

×:Swelling stripping is generated when impregnating 10 seconds × 1 time, adaptation is insufficient.

< flexibilities (bend test after 260 DEG C of soft solder Reflow Solderings) >

For making above-mentioned evaluation substrate, by 3 test films, be used in advance highest setting is 260 DEG C of reflow soldering Test method below evaluates bending.

It in the state that test film is bent to 180 ° in such a way that cured coating film becomes outside, is clamped, is born with 2 tablets After load load G (the standard volume copper of 1kg) makes it bend for 10 seconds, using light microscope, the cured coating film portion of bending part is confirmed In whether crack, recycled the action as 1, number of record when cracking.Evaluation criteria is for example following.

◎:Bend 20 times or more.

○:10 times are bent less than 20 times.

△:5 times are bent less than 10 times.

×:Bending is less than 5 times.

By these evaluation result is shown in table 6.

&#91;Table 6&#93;

The evaluation result shown in above-mentioned table clearly confirms, in the laminate structure of each embodiment, in excellent development On the basis of property and heat resistance, good flexibility can also be obtained after soft solder Reflow Soldering.

Then, the resin combination to the resin layer (B) for constituting above-described embodiment 2-5, the formation with above-mentioned resin layer (B) Similarly film is formed on the flexible printed wiring base material that thick 18 μm of the formation of copper has circuit.For gained film, in evaluation State resolution ratio, heat resistance, flexibility.By it evaluation result is shown in table 7.

&#91;Table 7&#93;

Claims (10)

1. a kind of hardening resin composition, which is characterized in that contain:Alkali-soluble polyimide resin;The polyimides tree Alkali-soluble resin other than fat;With curability compound.

2. hardening resin composition according to claim 1, wherein alkali-soluble other than the polyimide resin Resin is polyamide-imide resin.

3. hardening resin composition according to claim 2, wherein the polyamide-imide resin is with following The polyamide-imide resin of structure shown in structure and the following general formula (2) shown in general formula (1),

X₁It is derived from the residue of the aliphatic diamine (a) for the dimeric dibasic acid that carbon number is 24~48, X₂For the aromatic diamine with carboxyl (b) residue, Y are each independently cyclohexane ring or aromatic rings.

4. hardening resin composition described in any one of claim 1 to 3, also contains core shell rubber particles.

5. hardening resin composition according to any one of claims 1 to 4, wherein the polyimide resin tool There is carboxyl.

6. hardening resin composition according to claim 5, wherein the polyimide resin has carboxyl and phenol Hydroxyl.

7. according to hardening resin composition according to any one of claims 1 to 6, wherein the curability compound is Epoxy resin.

8. a kind of laminate structure, which is characterized in that it has:Resin layer (A);With the sandwiched resin layer (A) is laminated in base material On resin layer (B),

The resin layer (B) is formed by hardening resin composition according to any one of claims 1 to 7, and the resin Layer (A) is formed by the alkali developable resin combination comprising alkali soluble resins and heat reactivity compound.

9. a kind of solidfied material, which is characterized in that by hardening resin composition according to any one of claims 1 to 7 or power Profit requires the laminate structure described in 8 to be formed.

10. a kind of electronic unit, which is characterized in that have the insulating film formed by the solidfied material described in claim 9.