CN107922615A

CN107922615A - Makrolon imide resin and the paste for having used it

Info

Publication number: CN107922615A
Application number: CN201680034895.8A
Authority: CN
Inventors: 内山翔子; 青山知裕
Original assignee: Toyobo Co Ltd
Current assignee: Toyobo Co Ltd
Priority date: 2015-10-19
Filing date: 2016-10-07
Publication date: 2018-04-17
Anticipated expiration: 2036-10-07
Also published as: KR102233604B1; TW201730240A; KR20180072591A; TWI697514B; WO2017068999A1; CN107922615B

Abstract

The present invention provides a kind of while meets (1) non-nitrogen series solvent dissolubility, (2) low warpage properties, (3) resistance to bend(ing) and the applicable makrolon imide resin paste for making solder mask layer, sealer or adhesive linkage.A kind of makrolon imide resin (A), it is characterised in that contain：The constituent shown in constituent, specific structure formula (2) shown in specific structure formula (1) and the constituent shown in specific structure formula (3), when whole constituents are set to 200 moles of %, constituent shown in specific structure formula (1) is 10 moles of more than %, constituent shown in specific structure formula (2) more than 30 moles of % and is less than 70 moles of %, more than 50 moles % of constituent shown in specific structure formula (3).

Description

Makrolon imide resin and the paste for having used it

Technical field

The present invention relates to makrolon imide resin and the paste obtained using it.Especially, it is related to for COF substrates Purposes is useful and has excellent heat resistance, flexibility and is suitable for the coating methods such as printing machine, distributor or spin coater Makrolon imide resin paste, and have solder mask layer, sealer or adhesive linkage obtained by the paste curing Electronic unit.

Background technology

In general, the heat resistance of polyimides system resins, insulating properties and chemical reagent resistance etc. are excellent, therefore extensive Insulating materials as electric/electronic device.Especially, it is used as the raw material of COF substrates mostly, and is applied to softness Property, the distribution plate material of small spatial electronic equipment, mounting substrate material.Be widely used in such as liquid crystal display, The display device used in gas ions display, organic el display etc. is set with equipments assembly base plate, smart mobile phone, tablet computer Junction cable, Operation switch portion substrate or these substrates between the substrate of standby terminal, digital camera, pocket game machine etc. Covering layer material (protective layer of circuit) etc..Especially, in the printed circuit boards, it is wide as the permanent protection overlay film of circuit It is general to use solder resist.Solder resist forms overlay film in the whole face in addition to the part welded of circuit conductor, and On printed circuit board (PCB) during wired electronic component, it is used as preventing solder attachment in unwanted part and prevents that circuit is direct Exposed to the protection overlay film of air.

However, the solder mask layer, sealer or adhesive linkage as the inscape of COF substrates are mostly with solution morphology It is coated, prints, therefore, as its material, it is proposed that includes the cooperation for the closed loop polyimide type resin for dissolving in solvent Thing, however, having used n-methyl-2-pyrrolidone contour as the solvent of the varnish for polyimides system resins in the past Boiling point nitrogen series solvent, therefore there are following problems：More than 200 DEG C of high temperature is needed to cure work for a long time in dried/cured Heat deterioration occurs for sequence, electronic unit.

And then the usual elasticity modulus of polyimides system resins is high and hard, therefore when being laminated in film, copper foil when base material, Warpage etc. occurs because of the difference of elasticity modulus, therefore there are problem in terms of rear process.In addition, cured film, which exists, lacks softness Property, the problem of bendability is poor.

In addition, as dissolve in non-nitrogen series solvent, make resin realize flexibleization and low elastic modulus forms have it is low The polyimides system resins of warpage and flexibility, for example, (patent document 1), (patent document 2) etc. disclose it is polysiloxane-modified Polyimides system resins.

Expensive is had dimethyl-silicon by these polysiloxane-modified polyimides system resins for low elastic modulus The diamines of oxygen alkane key is used as starting material, less economical.In addition, with the increase of polysiloxanes copolymerization amount, there are adaptation, resistance to The problem of solvent borne, chemical reagent resistance reduce.

In addition, disclose by mixing a certain amount of polycarbonate resin into polyimide resin to assign flexibility, Improve composition (patent document 3), (patent document 4) of the shaping processability of resin combination.And then disclose pass through by Polyimide resin is mixed with epoxy resin and polycarbonate resin, improves the combinations of thermoplastic resins of shaping processability Thing (patent document 5).

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 7-304950 publications

Patent document 2：Japanese Unexamined Patent Publication 8-333455 publications

Patent document 3：Japanese Unexamined Patent Publication 5-320492 publications

Patent document 4：Japanese Unexamined Patent Publication 6-136267 publications

Patent document 5：Japanese Unexamined Patent Application 62-7758 publications

The content of the invention

Problems to be solved by the invention

However, they be as be suitable for melting mixing, melting extrusion resin and include, although heat resistance, machine Tool excellent strength, but non-nitrogen series solvent is not dissolved in, hardly it is with low warpage and flexibility.

As understood as the example, so far in the prior art, not yet obtain and meet (1) non-nitrogen system at the same time Solvent solubility, (2) low warpage properties, (3) resistance to bend(ing) and applicable make the poly- of solder mask layer, sealer or adhesive linkage Imide resin paste.

The present invention is carried out using the problem of the prior art as background.That is, it is an object of the present invention to provide (1) non-nitrogen series solvent dissolubility, (2) low warpage properties, (3) resistance to bend(ing) are excellent and heat resistance, chemical reagent resistance, electrical characteristics are excellent Different makrolon imide resin, and the makrolon imide resin paste obtained using it, and have above-mentioned paste The electronic unit of solder mask layer, sealer or adhesive linkage obtained by agent curing.

The method for solving problem

A kind of makrolon imide resin (A), it is characterised in that contain：Constituent, general formula shown in general formula (1) (2) constituent shown in constituent and formula (3) shown in, when whole constituents are set to 200 moles of %, general formula (1) 10 moles of more than %, the constituent shown in general formula (2) do not rub more than 30 moles of % and less than 70 the constituent shown in You are %, and more than 50 moles % of the constituent shown in formula (3).

[chemical formula 1]

(in general formula (1), A is the straight-chain alkyl-sub of the optionally substituent with carbon number 1~10.)

[chemical formula 2]

(in general formula (2), multiple R represent the divalent organic group of carbon number more than 1 independently of one another, n be more than 1 it is whole Number.)

[chemical formula 3]

A kind of makrolon imide resin (A), it is characterised in that with the double dehydration trimellitate of (a) aklylene glycol, (b) acid dianhydride and (c) o-tolidine diisocyanate (TODI) work with polycarbonate backbone shown in general formula (4) For necessary copolymer composition, by all acid into when being divided into 100 moles of %, (a) aklylene glycol pair is dehydrated trimellitates and is 10 moles of more than %, the acid dianhydride with polycarbonate backbone shown in (b) general formula (4) rub more than 30 moles of % and less than 70 Your %, also, when whole amine components are set to 100 moles of %, (c) o-tolidine diisocyanate (TODI) rubs more than 50 You are %.

[chemical formula 4]

(in general formula (4), multiple R represent the divalent organic group of carbon number more than 1 independently of one another, n be more than 1 it is whole Number.)

A kind of makrolon imide resin paste, it is characterised in that contain：Above-mentioned makrolon imide resin (A), Every 1 molecule has the epoxy resin (B) and filler (C) of more than 2 epoxy groups.

The thixotropic index of above-mentioned makrolon imide resin paste is preferably more than 1.2, additionally, it is preferred that being used for COF (Chip On Film)。

A kind of electronic unit, it has solder mask layer, table obtained by above-mentioned makrolon imide resin paste curing Face protective layer or adhesive linkage.

The effect of invention

Pass through the present invention, it is possible to provide (1) non-nitrogen series solvent dissolubility for being difficult to meet at the same time in the past, (2) low warpage properties, (3) the excellent makrolon imide resin of resistance to bend(ing) and the paste that is obtained using it and with aforesaid paste is cured Obtained by solder mask layer, sealer or adhesive linkage electronic unit.

Embodiment

Hereinafter, the makrolon imide resin and makrolon imide resin paste of the present invention are described in detail.

The makrolon imide resin (A) of the present invention is illustrated.The feature of makrolon imide resin (A) exists In it contains the constituent shown in general formula (1), the constituent shown in general formula (2) and the constituent shown in formula (3), will When whole constituents are set to 200 moles of %, the constituent shown in general formula (1) is 10 moles of more than %, shown in general formula (2) Constituent is more than 30 moles of % and is less than 70 moles of %, and more than 50 moles % of the constituent shown in formula (3).

[chemical formula 1]

(in general formula (1), A is the straight-chain alkyl-sub of the optionally substituent with carbon number 1~20.)

[chemical formula 2]

[chemical formula 3]

The makrolon imide resin (A) of the present invention can expect non-nitrogen by the constituent shown in containing general formula (1) The effect that series solvent dissolubility, heat resistance improve.In general formula (1), A is the carbon number more than 1 and less than 20 for optionally having substituent Straight-chain alkyl-sub, preferably carbon number be more than 2 and less than 10.During with substituent, substituent is preferably the alkyl of carbon number 1~3.

When whole constituents are set to 200 moles of %, the composition of makrolon imide resin (A) formula of (1) into The content divided is necessary for 10 moles of more than %.Preferably 20 moles of more than %, more preferably 30 moles of more than %.Additionally, it is preferred that For 90 moles of below %, more preferably 80 moles of below %, more preferably 70 moles of below %.During less than 10 moles of %, Sometimes non-nitrogen series solvent dissolubility, heat resistance can not be obtained, if being more than 90 moles of %, can not be contained sometimes with the amount of full The constituent shown in constituent, formula (3) shown in aftermentioned general formula (2).Therefore, (machinery is special for low warpage properties, resistance to bend(ing) Property) reduce sometimes.

Constituent shown in general formula (2) is because can be to the makrolon imide resin of the present invention with flexible (A) low warpage properties, non-nitrogen series solvent dissolubility etc. are assigned.

In general formula (2), multiple R represent the divalent organic group of carbon number more than 1 independently of one another.It is preferred that carbon number for more than 5, More preferably more than 10, it is preferably less than 20, more preferably less than 18.In addition, as divalent organic group, do not limit especially It is fixed, it is preferably the straight-chain alkyl-sub optionally with substituent, above-mentioned carbon number preferably also includes the carbon of substituent.In addition, n for 1 with On integer, be preferably more than 2 integer, more preferably more than 3 integer, be preferably less than 10 integer, more preferably 8 with Under integer.

When whole constituents are set to 200 moles of %, shown in the general formula (2) in makrolon imide resin (A) The content of constituent must be over 30 moles of %, be preferably 35 moles of more than %, more preferably 40 moles of more than %.In addition, 70 moles of % are have to be lower than, are preferably 65 moles of below %, more preferably 60 moles of below %.If 30 moles of below %, Warpage or the dissolubility in non-nitrogen series solvent then occurs in stacking sometimes to be reduced.Therefore, one is taken care of at 5 DEG C~30 DEG C It is possible to separate out resin within a month.On the other hand, if 70 moles of more than %, then resistance to bend(ing) (mechanical property), heat-resisting Property is likely to decrease.

As the constituent of makrolon imide resin (A), constituent and general formula shown in above-mentioned general formula (1) (2) total amount of the constituent shown in is preferably 60 moles of more than %, more preferably 65 moles of more than %, is more preferably 70 moles of more than %, particularly preferably 75 moles of more than %, be most preferably 80 moles of more than %.If very few, low warpage properties, Dissolubility in non-nitrogen series solvent reduces sometimes.

The makrolon imide resin (A) of the present invention containing the constituent shown in formula (3) by that can show Excellent resistance to bend(ing).

When whole constituents are set to 200 moles of %, the structure shown in formula (3) in makrolon imide resin (A) Content into component must be over 50 moles of %, be preferably 60 moles of more than %, more preferably 70 moles of more than %, further excellent Elect 80 moles of more than %, particularly preferably 90 moles of more than % as, be most preferably 100 moles of %.If 50 moles of below %, Resistance to bend(ing) then will not be fully shown sometimes.

Above-mentioned general formula (1) of the makrolon imide resin (A) containing specified quantitative of the present invention, general formula (2) and formula (3) Constituent.Therefore, makrolon imide resin (A) is preferably logical with the double dehydration trimellitates of (a) aklylene glycol, (b) Acid dianhydride with polycarbonate backbone and (c) o-tolidine diisocyanate shown in formula (4) is as necessary copolymerization Component, by all acid into when being divided into 100 moles of %, it is preferred that the double dehydration trimellitates of (a) aklylene glycol rub for 10 You are more than %, and the acid dianhydride with polycarbonate backbone shown in (b) general formula (4) more than 30 moles of % and is less than 70 moles of %, Also, when whole amine components are set to 100 moles of %, more than 50 moles % of (c) o-tolidine diisocyanate.

[chemical formula 4]

<(a) the double dehydration trimellitates of aklylene glycol>

As (a) component for forming the makrolon imide resin (A) used in the present invention, it is necessary to be (a) alkylidene The double dehydration trimellitates (hereinafter also referred to as (a) component) of glycol.Trimellitates are dehydrated by using aklylene glycol is double, It can expect non-nitrogen series solvent dissolubility, the excellent effect of heat resistance.

As the concrete example of the double dehydration trimellitates of aklylene glycol, it is not particularly limited, methylene two can be included The double dehydration trimellitates of alcohol, the double dehydration trimellitates (TMEG) of ethylene glycol, the double dehydration trimellitates of propane diols, Isosorbide-5-Nitrae-fourth The double dehydration trimellitate of glycol, the double dehydration trimellitates of hexamethylene glycol, the double dehydration trimellitates of polyethylene glycol or Double dehydration trimellitates of person's polypropylene glycol etc., they may be used singly or in combin two or more.From availability Viewpoint is set out, wherein it is preferred that the double dehydration trimellitates (TMEG) of ethylene glycol.

The all acid of object will be reacted into when being divided into 100 moles of %, the copolymerization amount of (a) component be necessary for 10 moles of % with On.Preferably 20 moles of more than %, more preferably 30 moles of more than %.Additionally, it is preferred that it is 90 moles of below %, further preferred For 80 moles of below %, particularly preferably 70 moles of below %.During less than 10 moles of %, it is molten that non-nitrogen series solvent can not be obtained sometimes Aftermentioned (b), (c) component, if being more than 90 moles of %, can not be copolymerized by Xie Xing, heat resistance with the amount of full sometimes.Cause This, low warpage properties, resistance to bend(ing) (mechanical property) reduce sometimes.

<(b) acid dianhydride with polycarbonate backbone shown in general formula (4)>

Forming shown in (b) general formula (4) of the makrolon imide resin (A) of the present invention has polycarbonate backbone Acid dianhydride (hereinafter also referred to as (b) component) is used as and assigns low warpage properties to makrolon polyimide resin (A), non-nitrogen is molten The flexible component of agent dissolubility etc. and be copolymerized.

It is the acid dianhydride with polycarbonate backbone shown in general formula (4) as (b) component.

[chemical formula 4]

In general formula (4), multiple R represent the divalent organic group of carbon number more than 1 independently of one another.It is preferred that carbon number for more than 5, More preferably more than 10, it is preferably less than 20, more preferably less than 18.In addition, as divalent organic group, do not limit especially It is fixed, it is preferably straight chain or optionally there is the alkylidene of substituent, above-mentioned carbon number preferably also includes the carbon of substituent.In addition, n is 1 Integer above, preferably more than 2 integer, more preferably more than 3 integer, preferably less than 10 integer, more preferably 8 Following integer.

Polycarbonate glycol for synthesizing (b) that is used in present invention component can have a variety of alkylenes in its skeleton The polycarbonate glycol (copolymerization polycarbonate glycol) of base, as commercially available product, can include such as Kuraray polyol C- 1015N, the Kuraray polyol C-1065N (carbonate diols of Kuraray Co., Ltd.s manufacture：2- methyl isophthalic acids, 8- pungent two Alcohol/1,9- nonanediol, number-average molecular weight are about 1,000), Kuraray polyol C-2015N, Kuraray polyol C- 2065N (the carbonate diols of Kuraray Co., Ltd.s manufacture：2- methyl isophthalic acids, 8- ethohexadiols/1,9- nonanediol, the equal molecule of number Amount about 2,000), Kuraray polyol C-1050, Kuraray polyol C-1090 (Kuraray Co., Ltd.s manufacture Carbonate diol：3- methyl isophthalic acids, 5- pentanediols/1,6- hexylene glycol, number-average molecular weight are about 1,000), Kuraray polyol C-2050, the Kuraray polyol C-2090 (carbonate diols of Kuraray Co., Ltd.s manufacture：3- methyl isophthalic acids, 5- penta 2 Alcohol/1,6- hexylene glycol, number-average molecular weight are about 2,000), DURANOL (registration mark)-T5650E (Asahi Chemical Industry's chemistry strain formula meetings The polycarbonate glycol of society's manufacture：1,5-PD/1,6- hexylene glycol, number-average molecular weight be about 500), DURANOL (registrars Mark)-T5651 (polycarbonate glycol of Asahi Chemical Corp's manufacture：1,5-PD/1,6- hexylene glycol, the equal molecule of number Amount about 1,000), DURANOL (registration mark)-T5652 (Asahi Chemical Corp manufacture polycarbonate glycol：1, 5- pentanediols/1,6- hexylene glycol, number-average molecular weight are about 2,000) etc..

As the method for manufacture (b) component, it is not particularly limited, can be by using known reaction method by trimellitic acid Acid anhydride acyl chlorides and above-mentioned diol compound synthesize.More specifically, first to the Trimellitic Anhydride Chloride solution for being dissolved in solvent Middle input diol compound and deoxidier, and stir 0.5~24 it is small when.Carried out under -20~50 DEG C of reaction temperature, from reaction From the viewpoint of selectivity, carried out more preferably at 20~40 DEG C.As Trimellitic Anhydride Chloride and diol compound Reactive ratio, using more than 2 moles of Trimellitic Anhydride Chloride and makes its reaction preferably with respect to 1 mole of diol compound.Anti- Solute concentration in answering carries out preferably in 5~80 weight %, more preferably in the range of 40~60 weight %.By anti- The hydrochloride of precipitation, and concentrated solvent are filtered after answering, can obtain that there is poly- carbonic acid as shown in the general formula (4) of target The acid dianhydride (the hereinafter also referred to tetracarboxylic dianhydride containing polycarbonate backbone) of ester skeleton.

By all acid into when being divided into 100 moles of %, the copolymerization amount of (b) component must be over 30 moles of %, be preferably 35 Mole more than %, more preferably 40 moles of more than %.It is preferably 65 moles of below %, more excellent further it is necessary to be less than 70 moles of % Elect 60 moles of below % as.If 30 moles of below %, then elasticity modulus will not be reduced fully sometimes, be sent out sometimes in stacking Raw warpage or the dissolubility in non-nitrogen series solvent reduce.Therefore, it is possible to analyse within taking care of one month at 5 DEG C~30 DEG C Go out resin.On the other hand, if 70 moles of more than %, then can not be contained with the amount of full above-mentioned (a) component, aftermentioned (c) into Point, therefore, resistance to bend(ing) (mechanical property), heat resistance reduce sometimes.

As the sour component of makrolon imide resin (A), above-mentioned (a) component and the total amount of (b) component are preferably 60 moles of more than %, more preferably 65 moles of more than %, more preferably 70 moles of more than %, particularly preferably 75 moles of % Above, it is most preferably 80 moles of more than %.If very few, low warpage properties, the dissolubility in non-nitrogen series solvent reduce sometimes.

As other sour components, 3 yuan or 4 yuan of the polycarboxylic acid derivatives with anhydride group can be used.As virtue Fragrant race's polycarboxylic acid derivatives, are not particularly limited, can include for example trimellitic anhydride (TMA), pyromellitic acid dianhydride, 3,3 '- 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ' -4,4 '-biphenyl tetracarboxylic dianhydride, 1,2,5,6- naphthalene tetracarboxylic acid dianhydrides, Isosorbide-5-Nitrae, 5, 8- naphthalene tetracarboxylic acids dianhydride, 2,3,5,6- pyridine tetracarboxylic dianhydrides, 3,4,9,10- tetracarboxylic dianhydrides, 3,3 ', 4,4 '-diphenyl Sulfone tetracarboxylic dianhydride, meta-terphenyl base -3,3 ', 4,4 '-tetracarboxylic dianhydride, 4,4 '-epoxide, two O-phthalic acid dianhydride, 1,1,1, Double (2,3- or 3, the 4- dicarboxyphenyi) propane dianhydrides of 3,3,3- hexafluoros -2,2-, 2,2- are double (2,3- or 3,4- dicarboxyphenyi) Propane dianhydride, 2,2- double [4- (2,3- or 3,4- di carboxyl phenyloxy) phenyl] propane dianhydride, 1,1,1,3,3,3- hexafluoros -2,2- Double (3, the 4- dicarboxyphenyis) -1,1,3 of double [4- (2,3- or 3,4- di carboxyl phenyloxy) phenyl] propane dianhydrides or 1,3-, 3- tetramethyl disiloxane dianhydrides etc..

In addition, as aliphatic or alicyclic polycarboxylic acid's derivative, it is not particularly limited, such as butane -1 can be included, 2,3,4- tetracarboxylic dianhydrides, pentane -1,2,4,5- tetracarboxylic dianhydrides, cyclobutane tetracarboxylic dianhydride, hexahydro pyromellitic acid dianhydride, ring Hex- 1- alkene -2,3,5,6- tetracarboxylic dianhydrides, 3- cyclohexyl -1- alkene -3- (1,2), 5,6- tetracarboxylic dianhydrides, 1- methyl -3- second Butylcyclohexane -3- (1,2), 5,6- tetracarboxylic dianhydrides, 1- methyl -3- cyclohexyl -1- alkene -3- (1,2), 5,6- tetrabasic carboxylic acids two Acid anhydride, 1- ethyl cyclohexanes -1- (1,2), 3,4- tetracarboxylic dianhydrides, 1- propyl cyclohexanes -1- (2,3), 3,4- tetracarboxylic dianhydrides, 1, 3- dipropyl butylcyclohexane -1- (2,3), 3- (2,3)-tetracarboxylic dianhydride, dicyclohexyl -3,4 are 3 ', 4 '-tetracarboxylic dianhydride, bicyclic [2,2,1] heptane -2,3,5,6- tetracarboxylic dianhydrides, 1- propyl cyclohexanes -1- (2,3), 3,4- tetracarboxylic dianhydrides, 1,3- dipropyl Hexamethylene -1- (2,3), 3- (2,3)-tetracarboxylic dianhydride, dicyclohexyl -3,4,3 ', 4 '-tetracarboxylic dianhydride, bicyclic [2,2,1] heptan Alkane -2,3,5,6- tetracarboxylic dianhydrides, bicyclic [2,2,2] octane -2,3,5,6- tetracarboxylic dianhydrides, bicyclic [2,2,2] octyl- 7- alkene - 2,3,5,6- tetracarboxylic dianhydrides or hexahydro trimellitic anhydride etc..

These 3 yuan and/or 4 yuan polycarboxylic acid derivatives with anhydride group may be used alone, can also be used in combination It is two or more.By acid into when being divided into 100 moles of %, 3 yuan and/or 4 yuan of the polycarboxylic acid derivatives with anhydride group are preferably 40 moles of below %, more preferably 35 moles of below %, more preferably 30 moles of below %, particularly preferably 25 moles of % Below, it is most preferably 20 moles of below %.

In addition, in the range of target capabilities are not damaged, can further be copolymerized as needed aliphatic, it is alicyclic, Aromatic dicarboxylic acid class.As aliphatic dicarboxylic acid, such as succinic acid, glutaric acid, adipic acid, suberic acid, nonyl two can be included Acid, decanedioic acid, decane diacid, dodecanedioic acid, eicosane diacid, 2- dimethyl succinic acids, 2- methyl adipic acid, 3- methyl oneself two Acid, 3- methylpentanes dicarboxylic acids, 2- methyloctanes dicarboxylic acids, 3,8- dimethyl decanes dicarboxylic acids, 3,7- dimethyl decane dicarboxyls Acid, 9,12- dimethyl eicosanes dicarboxylic acids, fumaric acid, maleic acid, dimeric dibasic acid, hydrogenated dimer acids etc.；As alicyclic dicarboxyl Acid, can include such as Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, 1,3- cyclohexane dicarboxylic acids, 1,2- cyclohexane dicarboxylic acids, 4,4 '-two hexamethylenes Base dicarboxylic acids etc.；As aromatic dicarboxylic acid, such as M-phthalic acid, terephthalic acid (TPA), phthalic acid, naphthalene two can be included Carboxylic acid, epoxide dibenzoic acid, stilbenedicarboxylicacid acid etc..These omega-dicarboxylic acids may be used alone, can also be used in combination two More than kind.If it is considered that in terms of heat resistance, adaptation, dissolubility, cost etc., then preferred decanedioic acid, Isosorbide-5-Nitrae-hexamethylene dicarboxyl Acid, dimeric dibasic acid, M-phthalic acid.

<(c) o-tolidine diisocyanate>

(c) component for forming the makrolon imide resin (A) of the present invention is (following with o-tolidine diisocyanate Also referred to as TODI) it is used as essential component.By using o-tolidine diisocyanate, excellent resist bending can be shown Property.

When whole amine components are set to 100 moles of %, (c) o-tolidine diisocyanate copolymerization amount must be over 50 and rub You are %, is preferably 60 moles of more than %, more preferably 70 moles of more than %, more preferably 80 moles of more than %, especially excellent Elect 90 moles of more than % as, be most preferably 100 moles of %.If 50 moles of below %, then sometimes the value of elasticity modulus be lower, Resistance to bend(ing) will not fully be shown.

, as needed can be with the range of target capabilities are not damaged in the makrolon imide resin (A) of the present invention Further copolymerization has isocyanate compound.As long as isocyanate compound is just not particularly limited, aromatic series can be included Polyisocyanates, aliphatic polyisocyante or alicyclic polyisocyanates.Preferably using aromatic polyisocyanate.Without spy Do not limit, specifically, in aromatic polyisocyanate, such as diphenyl methane -2 can be included, 4 '-diisocyanate, 3, 2 '-or 3,3 '-or 4,2 '-or 4,3 '-or 5,2 '-or 5,3 '-or 6,2 '-or 6,3 '-dimethyl diphenylmethane -2,4 '-two Isocyanates, 3,2 '-or 3,3 '-or 4,2 '-or 4,3 '-or 5,2 '-or 5,3 '-or 6,2 '-or 6,3 '-diethyl diphenylmethyl Alkane -2,4 '-diisocyanate, 3,2 '-or 3,3 '-or 4,2 '-or 4,3 '-or 5,2 '-or 5,3 '-or 6,2 '-or 6,3 '-diformazan Epoxide diphenyl methane -2,4 '-diisocyanate, diphenyl methane -4,4 '-diisocyanate, diphenyl methane -3,3 '-two Isocyanates, diphenyl methane -3,4 '-diisocyanate, diphenyl ether -4,4 '-diisocyanate, UVINUL MS 40,4 '-two Isocyanates, diphenyl sulfone -4,4 '-diisocyanate, Toluene-2,4-diisocyanate, 4- diisocyanate, Toluene-2,4-diisocyanate, 6- diisocyanate, Benzene dimethylene diisocyanate, terephthalylidene diisocyanate, naphthalene -2,6- diisocyanate, 4,4 '-[2,2 couples of (4- Phenoxyphenyl) propane] diisocyanate, 3,3 '-or 2,2 '-diethyl biphenyl base -4,4 '-diisocyanate, 3,3 '-diformazan Epoxide xenyl -4,4 '-diisocyanate, 3,3 '-diethoxy xenyl -4,4 '-diisocyanate etc..In view of heat-resisting Property, be preferably diphenyl methane -4 in terms of adaptation, dissolubility, cost etc., 4 '-diisocyanate (MDI), Toluene-2,4-diisocyanate, 4- bis- Isocyanates (TDI), m-xylylene diisocyanate, more preferably Toluene-2,4-diisocyanate, 4- diisocyanate (TDI).It Can be used alone, or two or more is applied in combination.

It is any of the above-described when the amine component used in the makrolon imide resin (A) of the present invention is set to 100 moles of % Kind isocyanate compound is preferably 100 moles of %.If replaced using diamine compound corresponding with above-mentioned isocyanates Above-mentioned isocyanates, then as makrolon polyimide resin precursor and via polyamic acid.If via polyamic acid, After the paste containing polyamic acid then is coated on the substrates such as COF (Chip On Film), it is often necessary to more than 200 DEG C or so High temperature carry out imidizate, it is possible to make COF occur heat deterioration, in addition, being restricted sometimes in equipment aspect.The present invention In, since the isocyanate compound comprising TODI is used only in amine component, can compared with the paste containing polyamic acid Handled with lower temperature, there is no problem as described above, so it is preferred that.

In addition, in addition to (b) component, in the range of target capabilities are not damaged, can also further be total to as needed It is poly- to have other flexible components.Such as aliphatic/aromatic polyester-diol class can be included, and (Co. Ltd. system, business spin in Japan Name of an article VYLON (registration mark) 220), aliphatic/aromatic polycarbonate glycol class (DAICELCHEMICAL INDUSTRIES, LTD. system, trade name PLACCEL (registration mark)-CD220, Kuraray Co., Ltd.s system, trade name C- 1015N, C-1050, C-1065N, C-1090, C-2015N, C-2065N, C-2090 etc., Asahi Chemical Corp's system, business Name of an article Duranol (registration mark) T-4671, T-4672, T-5650E, T-5650J, T-5651, T5652 etc.), polycaprolactone two Alcohols (DAICEL CHEMICAL INDUSTRIES, LTD. system, trade name PLACCEL (registration mark) -220 etc.), carboxyl change Property acrylonitrile butadiene rubber class (Ube Industries, Ltd's system, trade name HyproCTBN1300 × 13 etc.), poly dimethyl silicon Polyorganosiloxane ramification of oxygen alkane glycol, polymethylphenylsiloxane glycol, carboxy-modified dimethyl silicone polymer class etc etc..

Makrolon imide resin (A) is by the polycarboxylic acid component ((a) component and (b) component) with anhydride group and different Isocyanate component ((c) component) manufactures (isocyanic acid ester process).

In isocyanic acid ester process, on the use level of (a) component, (b) component and (c) component, preferably make anhydride group number with The ratio of isocyanate groups number is isocyanate groups number/anhydride group number=0.8~1.2.When above-mentioned ratio is less than 0.8, Sometimes be difficult to improve makrolon imide resin (A) molecular weight, sometimes heat resistance, resistance to bend(ing) reduce or film compared with It is crisp.In addition, when above-mentioned ratio is higher than 1.2, the viscosity of makrolon imide resin (A) becomes higher sometimes, and the situation of ink is made Under printing when misplacing of stencil be deteriorated sometimes.

The polymerisation of the makrolon imide resin (A) used in the present invention preferably carries out under non-nitrogen series solvent. Specifically, preferably in 1 in the group being made of ether series solvent, ester series solvent, ketone series solvent and aromatic hydrocarbon series solvent In the presence of kind above organic solvent, such as in isocyanic acid ester process, while removing the free dioxy produced from reaction system Change carbon gas while making its heat condensation, so as to carry out above-mentioned polymerisation.

As above-mentioned solvent, it is not particularly limited, ether series solvent can include such as diethylene glycol dimethyl ether (diethylene glycol (DEG) Dimethyl ether), diethylene glycol diethyl ether (diethyl carbitol), triethylene glycol dimethyl ether (triglyme), three second two Alcohol Anaesthetie Ether (triethylene glycol diethyl ether) etc.；Ester series solvent can be included such as gamma-butyrolacton, cellosolve acetate；Ketone system is molten Agent can be included such as methyl iso-butyl ketone (MIBK), cyclopentanone, cyclohexanone, isophorone；Aromatic hydrocarbon series solvent can include example Such as toluene, dimethylbenzene, SOLVESSO.They may be used alone, can also be used in combination two or more.

When manufacturing makrolon imide resin (A), generated makrolon acid imide can be dissolved by preferably selecting use The solvent of resin (A), further preferably using the solvent being adapted to after polymerisation directly as makrolon imide resin paste The solvent used.Numerous and diverse operation such as operation in this way, displacement solvent disappears, and can inexpensively be manufactured.It is in addition, molten The boiling point of agent is preferably more than 140 DEG C and less than 230 DEG C.During less than 140 DEG C, the solvent in polymerisation is possible to volatilize, separately During outer progress such as silk-screen printing, there is a possibility that solvent quickly volatilizees, version blocking plug occurs.If it exceeds 230 DEG C, then sometimes It is difficult to assign low temperature drying/curability.In order to assign higher volatility, low temperature drying/curability, and varnish stability It is excellent, efficiently reacted in homogeneous system, preferably gamma-butyrolacton, cyclohexanone, diethylene glycol dimethyl ether or triethylene glycol Dimethyl ether.

The dosage of solvent be preferably set to generated makrolon imide resin (A) 0.8~5.0 times (mass ratio), More preferably it is set to 0.9~2.0 times.During less than 0.8 times, there are viscosity during synthesis it is excessive, be difficult to what is synthesized because that can not stir Tendency, if it exceeds 5.0 times, then there are the tendency that reaction speed reduces.

In isocyanic acid ester process, reaction temperature is preferably set to 60~200 DEG C, is more preferably set to 100~180 DEG C.Less than 60 DEG C When, there is the reaction time to become long, if it exceeds 200 DEG C, then the decomposition of monomer component is likely to occur in reacting.In addition, Three dimensional stress reaction easily occurs and causes gelation.Reaction temperature can divide multiple stages to carry out.Reaction time can be according to batch Scale, use reaction condition, especially reaction density come suitably select.

, can also be in triethylamine, lutidines, picoline, 11 carbon in order to promote to react in isocyanic acid ester process Alkene, triethylene diamine (Isosorbide-5-Nitrae-diazabicyclo [2,2,2] octane), DBU (1,8- diazabicyclo [5,4,0] -7-, 11 carbon Alkene) etc. the alkali metal such as amine, lithium methoxide, sodium methoxide, sodium ethoxide, butanol potassium, potassium fluoride, sodium fluoride, alkaline earth metal compound or Carried out in the presence of the catalyst such as the metals such as person's titanium, cobalt, tin, zinc, aluminium, semi metallic compound.

If including an example of the manufacture method of makrolon imide resin (A), can make (a) component and (b) into Divide, condensation reaction (polyimides) occurs for (c) component to obtain.It is illustrated below go out the present invention makrolon imide series tree The manufacture method of fat, but the present invention is not limited thereto.

By adding (a) component, (b) component, (c) component, polymerization catalyst, polymer solvent into reaction vessel and dissolving Afterwards, stir while more than when reaction 5 is small at 80~190 DEG C, preferably 100~180 DEG C, then use poly- under stream of nitrogen gas Untill bonding solvent is diluted to appropriate solvent viscosity, and cooled down, the makrolon imide resin of target can be obtained (A)。

The makrolon imide resin (A) used in the present invention preferably has and 0.1 in gamma-butyrolacton, at 30 DEG C The suitable molecular weight of the log viscosities of~2.0dl/g, more preferably has the molecule suitable with the log viscosities of 0.2~1.5dl/g Amount.When log viscosities are less than 0.1dl/g, heat resistance reduces sometimes or film is more crisp.In addition, sometimes the viscosity of paste become it is strong, Misplacing of stencil is deteriorated.On the other hand, if it exceeds 2.0dl/g, then be difficult to be dissolved in solvent, easily occur in polymerization it is insoluble.In addition, Sometimes the viscosity of varnish becomes higher and is difficult to operate, or is reduced with the adaptation of base material.

The glass transition temperature of the makrolon imide resin (A) used in the present invention is preferably more than 20 DEG C, into One step is preferably more than 60 DEG C.During less than 20 DEG C, it is possible to which heat resistance deficiency or resin stick together.The upper limit does not limit especially It is fixed, it is preferably less than 300 DEG C from the viewpoint of solvent solubility.

(B) that is used in the present invention as long as every 1 molecule of the epoxy resin of component has the asphalt mixtures modified by epoxy resin of more than 2 epoxy groups Fat is just not particularly limited.As epoxy resin (B), it is not particularly limited, such as Mitsubishi chemical Co., Ltd's system can be included The bisphenol A type epoxy resins such as the trade name jER (registration mark) 828,1001 made；The trade name of Toto Kasei KK's manufacture The bisphenol-A epoxy resins such as ST-2004,2007；The trade name YDF-170 of Toto Kasei KK's manufacture, 2004 etc. Bisphenol f type epoxy resin；Trade name YDB-400, the brominated bisphenol a type epoxy resin such as 600 of Toto Kasei KK's manufacture； The trade name jER (registration mark) 152 of Mitsubishi chemical Co., Ltd's manufacture, 154,157S70,1032H60；Japanese chemical drug strain formula Trade name EPN (registration mark) -201, the BREN (registration mark) of commercial firm's manufacture；The Dow Chemical Company are manufactured The phenol novolak type epoxy such as trade name DEN-438；The trade name YDCN-702 of Toto Kasei KK's manufacture, 703； Trade name EOCN (registration mark) -125S, the o-cresol phenolic aldehyde type ring oxygen tree such as 103S, 104S of Nippon Kayaku K. K's manufacture Fat；The flexible epoxy resins such as the trade name YD-171 of Toto Kasei KK's manufacture；Yuka Shell Epoxy Co., Ltd.s The trade name Epon1031S of manufacture；Trade name Araldite (the registrations of Ciba Specialty Chemicals Inc. manufactures Trade mark) 0163；Trade name Denacol (registration mark) EX-611, EX- of Nagase Chemtex Corporation manufactures 614th, the polyfunctional epoxy resin such as EX-622, EX-512, EX-521, EX-421, EX-411, EX-321；Yuka Shell The trade name Epikote (registration mark) 604 of Epoxy Co., Ltd.s manufacture；The trade name of Toto Kasei KK's manufacture YH-434；Trade name TETRAD (registration mark)-X, the TETRAD- of Mitsubishi Gas Chemical Company manufactures C；The trade name GAN of Nippon Kayaku K. K's manufacture；The amine type rings such as the trade name ELM-120 of Sumitomo Chemical Co's manufacture Oxygen tree fat；Trade name Araldite (registration mark) PT810 of Ciba Specialty Chemicals Inc. manufactures etc. is containing miscellaneous The epoxy resin of ring；The trade name CELLOXIDE (registration mark) of Daicel Chemical Industries, Ltd. manufactures 2021st, EHPE (registration mark) 3150；The alicyclic epoxy resins such as the ERL4234 of UCC companies manufacture；Big Japanese ink chemistry work The bisphenol-s epoxy resins such as trade name EPICLON (registration mark) EXA-1514 of industry Co., Ltd. manufacture；Nissan Chemical Industries The triglycidyl isocyanurates such as the TEPIC (registration mark) of Co., Ltd.'s manufacture；Yuka Shell Epoxy Co., Ltd.s The union II toluene phenol-type epoxy resin such as trade name YX-4000 of manufacture；The commodity of Yuka Shell Epoxy Co., Ltd.s manufacture Bisphenol-type epoxy resins such as name YL-6056 etc., they can be used alone, or be applied in combination two or more.

Have among these epoxy resin, preferably in bisphenol A type epoxy resin, bisphenol f type epoxy resin, 1 molecule more Phenol novolak type epoxy, o-cresol phenol aldehyde type epoxy resin in 2 epoxy groups.In addition, amine type epoxy resin is non-halogen Prime system, from improve with the compatibility of makrolon imide resin (A), solvent resistance, chemical reagent resistance, moisture-proof viewpoint It is preferable to set out.

The dosage of the epoxy resin (B) used in the present invention is excellent relative to makrolon imide resin (A) 100 mass parts Elect 1~50 mass parts, particularly preferably more preferably 2~40 mass parts, 3~30 mass parts as.Epoxy resin (B's) matches somebody with somebody When resultant is less than 1 mass parts, there are the tendency that scolding tin heat resistance, solvent resistance, chemical reagent resistance, moisture-proof reduce, if More than 50 mass parts, then there are low warpage properties, mechanical property, heat resistance, varnish stability and with makrolon acid imide tree The tendency that the compatibility of fat (A) reduces.And then there are cured film lack flexibility, resistance to bend(ing) (mechanical property) reduce to incline To.

In epoxy resin (B) used in the present invention, as diluent, it can also further include and only have in 1 molecule There is the epoxide of 1 epoxy group.

As the adding method of epoxy resin (B), it is not particularly limited, the epoxy resin (B) that will can be added in advance It is added again after being dissolved in the solvent identical with the solvent included in makrolon imide resin (A), alternatively, it is also possible to straight Connect added in makrolon imide resin (A).

The filler (C) (hereinafter also referred to as (C) component) used in the present invention is preferably inorganic filler or organic filler.Make For filler (C), as long as forming paste in being dispersed in above-mentioned makrolon imide resin (A), and the paste can be assigned Thixotropy (thixotropy), is not particularly limited.That is, it is preferably capable the makrolon imide resin paste to the present invention Assign the inorganic filler or organic filler of thixotropy.As such inorganic filler, such as silica (SiO can be used₂、 The trade name AEROSIL (registration mark) of Japanese AEROSIL companies manufacture), aluminium oxide (Al₂O₃), titanium dioxide (TiO₂), oxygen Change tantalum (Ta₂O₅), zirconium oxide (ZrO₂), silicon nitride (Si₃N₄), barium titanate (BaOTiO₂), barium carbonate (BaCO₃), lead titanates (PbO·TiO₂), lead zirconate titanate (PZT), zirconium lanthanium titanate lead (PLZT), gallium oxide (Ga₂O₃), spinelle (MgOAl₂O₃), it is rich Mullite (3Al₂O₃·2SiO₂), green stone (2MgO2Al₂O₃·5SiO₂), talcum (3MgO4SiO₂·H₂O), aluminium titanates (TiO₂-Al₂O₃), the zirconium oxide (Y containing yittrium oxide₂O₃-ZrO₂), barium silicate (BaO8SiO₂), boron nitride (BN), calcium carbonate (CaCO₃), calcium sulfate (CaSO₄), zinc oxide (ZnO), magnesium titanate (MgOTiO₂), barium sulfate (BaSO₄), organise swelling Soil, carbon (C), Org-montmorillonite (the trade name Lucentite (registration mark) of Co-op Chemical Co., Ltd.s manufacture STN, Lucentite SPN, Lucentite SAN, Lucentite SEN) etc., they can be used alone, and can also combine Using two or more.From the viewpoint of tone, the imparting transparency, mechanical property, thixotropy from gained paste, preferably using two Silica, Lucentite.

As the inorganic filler used in the present invention, preferably average grain diameter be less than 50 μm, maximum particle diameter be less than 100 μm Particle diameter inorganic filler, average grain diameter is more preferably less than 20 μm, and average grain diameter is most preferably less than 10 μm.Carry herein And average grain diameter (median particle diameter) obtained using laser diffraction/scattering formula particle size distribution device according to volume reference Value.If average grain diameter, which more than 50 μm, is difficult to obtain, has abundant thixotropic paste, the bendability of film reduces sometimes. If maximum particle diameter is more than 100 μm, tendency that appearance, adaptation there are film become inadequate.

As the organic filler used in the present invention, formed as long as being dispersed in above-mentioned makrolon imide resin solution Paste, and thixotropy can be assigned to the paste, polyimide resin particle, benzoguanamine resin can be included Grain, epoxy particles etc..

By (A) into when being divided into 100 mass parts, the dosage of the filler (C) used in the present invention is preferably 1~25 mass Part.More preferably 2~15 mass parts, particularly preferably 3~12 mass parts.The use level of inorganic filler or organic filler is low When 1 mass parts, there are the tendency that printing reduces, if it exceeds 25 mass parts, then there are the machinery such as bendability of film is special Property, the transparency reduce tendency.

, can be to the makrolon of the present invention in order to further improve the characteristics such as adaptation, chemical reagent resistance, heat resistance Curing accelerator is added in imide resin paste.As long as the curing accelerator used in the present invention can promote above-mentioned poly- carbonic acid The curing reaction of ester imide resin (A), epoxy resin (B), is not particularly limited.

As the concrete example of such curing accelerator, such as Shikoku Chem's manufacture can be included 2MZ、2E4MZ、C11Z、C17Z、2PZ、1B2MZ、2MZ-CN、2E4MZ-CN、C11Z-CN、2PZ-CN、2PHZ-CN、2MZ-CNS、 2E4MZ-CNS、2PZ-CNS、2MZ-AZINE、2E4MZ-AZINE、C11Z-AZINE、2MA-OK、2P4MHZ、2PHZ、2P4BHZ Deng imdazole derivatives；The guanamines such as acetylguanamine, benzoguanamine；Diaminodiphenyl-methane, m-phenylene diamine (MPD), meta-xylene two More amines such as amine, diamino diphenyl sulfone, dicyandiamide, urea, urea derivative, melamine, polynary hydrazides；Their acylate And/or amine complex, ethyl diaminourea-S- triazines, 2,4- diaminourea-S- triazines, 2, the 4- bis- of epoxy adduct, boron trifluoride The triazine derivatives species such as amino -6- xylyl-S- triazines；Trimethylamine, triethanolamine, N, N- dimethyl octylame, N- benzyls two Methylamine, pyridine, N-methylmorpholine, six (N- methyl) melamines, 2,4,6- tri- (dimethyl p-aminophenol), tetramethylguanidine, DBU The tertiary amines such as (1,8- diazabicyclo [5,4,0] -7- endecatylenes), DBN (1,5- diazabicyclo [4,3,0] -5- nonenes)； U-CAT (registration mark) SA1 (DBU- phenates) as their acylate, (DBU- is pungent by U-CAT (registration mark) SA 102 Hydrochlorate), U-CAT (registration mark) SA 831 (DBU- phenol novolacs salt), (four benzene of DBU systems of U-CAT (registration mark) 5002 Ylboronic acid ester salt) (being San-Apro Ltd. manufactures) and/or tetraphenyl borate salts, polyvinylphenol, polyvinylphenol Organic phosphines such as bromide, tributylphosphine, triphenylphosphine, three -2- cyano ethyl phosphines；Three normal-butyls (2,5- dihydroxy phenyl) bromine Change the quaternary phosphine salts such as Phosphonium, phosphonium hexadecanyl-3-butyl chloride, tetraphenylphosphoniphenolate tetraphenyl borate salts；Benzyltrimethylammonium chloride, benzene The quaternary ammonium salts such as base tributyl ammonium chloride；Above-mentioned multi-carboxy anhydride, diphenyl iodine tetrafluoroborate, triphenylsulfonium hexafluoro-antimonic acid Salt, 2,4,6- triphenyl thiapyran hexafluorophosphates, 261 (Ciba Specialty of Irgacure (registration mark) Chemicals Inc. are manufactured), the light cationic polymerization catalytic such as Optomer-SP-170 (ADEKA Corporation manufactures) Agent；The reaction with same mole thing of phenylethylene-maleic anhydride resin, phenyl isocyanate and dimethylamine；Toluene di-isocyanate(TDI), different Buddhist Reaction with same mole thing of the organic multiple isocyanates such as your ketone diisocyanate and dimethylamine etc..They can be used alone or group Close using two or more.Preferably have potential curability curing accelerator, can include DBU, DBN acylate and/ Or tetraphenyl borate salts, light cationic polymerization catalyst etc..

By (A) into when being divided into 100 mass parts, the dosage of curing accelerator is preferably 0~20 mass parts.If it exceeds 20 Mass parts, then the storage stability of makrolon imide resin composition, the heat resistance of film reduce sometimes.

The makrolon imide resin paste of the present invention is containing above-mentioned makrolon imide resin (A) component, ring The composition of oxygen tree fat (B) component and filler (C) component.And then as needed can be preferably other to coordinate with aforementioned proportion Gradation composition.It is preferred that obtained by the way that these each components are equably mixed with roller mill, mixer, triple-roller mill etc..Mixing As long as method can obtain fully dispersed method, just it is not particularly limited.Preferably utilize the multiple mixing of triple-roller mill.

On the makrolon imide resin paste of the present invention, Brookfield viscosimeter (hereinafter also referred to Type Bs are utilized Viscosimeter) viscosity that measures be preferably at 25 DEG C 50dPas~1000dPas scope, more preferably The scope of 100dPas~800dPas.If viscosity is less than 50dPas, the outflow of depositing paste after printing becomes larger, And the tendency of filming occurs for thickness.If viscosity is more than 1000dPas, there are following tendencies when printing：Paste is transferred to The transferability of base material reduces, while producing fuzzy, hole and pin hole increase in print film.

Thixotropic index (thixotropy) is also important.The thixotropic index of makrolon imide resin paste is in aftermentioned assay method In be preferably more than 1.2, more preferably more than 1.3.The upper limit is preferably less than 7.0, more preferably less than 6.0.Shake Variation be less than 1.2 when, deposit paste after printing outflow become larger and thickness generation filming tendency.If it exceeds 7.0, Then there are the tendency that paste stops flowing.Thixotropic index can be adjusted by the use level of (c) component for being used as thixotropic index imparting agent.

In the makrolon imide resin and paste of the present invention, phthalocyanine blue, phthalocyanine green, iodine can be used green as needed Usual colouring agent known in (iodine green), two diazonium Huangs, crystal violet, titanium oxide, carbon black, naphthalene are black etc.；It is hydroquinone, right Usual polymerization inhibitor known in benzenediol monomethyl ether, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, phenthazine etc.；Orben、Bentone、 Usual tackifier known in montmorillonite etc.；The defoamer of silicone-based, fluorine system, macromolecular etc.；Levelling agent；Imidazoles system, thiazole system, The coupling agent such as triazole system, organo-aluminum compound, organic titanic compound, organic silane compound/adaptation imparting agent；Phosphoric acid triphen Ester, tricresyl phosphate, tricresyl phosphate (dimethylbenzene) ester, triethyl phosphate, phosphate toluene diphenyl ester, phosphoric acid (dimethylbenzene) hexichol Double (2, the 6- dimethylbenzene) esters of ester, tricresyl phosphate, phosphoric acid 2- ethylhexyls, di(2-ethylhexyl)phosphate methyl formate, resorcinol are double, and (bisphenol-A is double Double (2- hydroxyethyls) the amino methyl phosphates of (two (tolyl)) phosphate, diethyl-N, N-, phosphamide, organo-phosphine oxide, The phosphorus flame retardants such as red phosphorus；Ammonium polyphosphate, triazine, melamine cyanurate, adipoguanamine, ethylenebis melamine, Three guanamines, cyanuric acid triazine salt, melem, melam, isocyanuric acid three (beta-cyano ethyl) ester, acetylguanamine, sulfuric acid amidino groups The nitrogenated flame retardants such as melamine, sulfuric acid melem, sulfuric acid melam；Diphenyl sulfone -3- potassium sulfonates, aromatic sulfonyl imines gold Belong to the metal salt flame retardants such as salt, polystyrolsulfon acid alkali metal salt；Aluminium hydroxide, magnesium hydroxide, dolomite, hydrotalcite, hydrogen The hydrated metal flame retardant such as barium monoxide, basic magnesium carbonate, zirconium hydroxide, tin oxide；Silica, aluminium oxide, iron oxide, oxygen Change titanium, manganese oxide, magnesia, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, antimony oxide, oxygen Change nickel, cupric oxide, tungsten oxide, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, stannic acid The inorganic flame retardants such as zinc；The fire retardant such as silicone powder/flame retardant；Heat stabilizer, antioxidant, lubricant etc it is known Usual additive kind.

The makrolon imide resin paste of the present invention can be used as such as solder resist and cure as follows, so that To solidfied material.That is, by the resin base material such as polyimide film plating coating copper and COF (Chip On Film) substrate for being formed On, the methods of using silk screen print method, spray-on process, rolling method, electrostatic coating processes, curtain coating, this is coated with 5~80 μm of thickness The makrolon imide resin paste of invention, and it is predrying film is carried out at 60~120 DEG C, then at 120~200 DEG C Lower progress trunk is dry.Drying can in atmosphere, can also be in not reactive atmosphere.Herein, as copper-plated to resin base material Method, the method that can be chemical plating or copper is sputtered to resin base material.

The layer of the makrolon imide resin paste of COF substrates becomes the welding resistance of COF substrates obtained from so operating Oxidant layer, sealer or adhesive linkage.Like this, makrolon imide resin paste of the invention forms material as overlay film Material, is useful for semiconductor element, various electronic component-use top coat ink, solder mask, in addition to this it is possible to be used as Coating, smears, bonding agent etc..Herein, solder mask layer refers in the whole in addition to the part welded of circuit conductor Face formed overlay film layer, and on a printed circuit wired electronic component when, be used as preventing solder attachment in unwanted Partly and circuit is prevented to be directly exposed to the protection overlay film of air.Sealer refers to the surface for being attached at circuit block And be used to protecting electronic unit from from manufacturing procedure, the mechanical influence of use environment, chemical affect protective layer.Adhesive linkage Refer to mainly carry out be bonded with film layer by metal layer and carry out the layer used during fitting processing.

Embodiment

In order to further illustrate the present invention, embodiment is exemplified below out, but the present invention is not limited to embodiment completely.Need It is noted that the measured value that embodiment is recorded is measured by following methods.

Makrolon imide resin (A) is dissolved in N- methyl -2- pyrroles in a manner of polymer concentration is 0.5g/dl Alkanone.The solution viscosity of the solution and solvent viscosity are measured using Ubbelohde type viscosimeter at 30 DEG C, and utilizes following formulas Calculated.

Log viscosities (dl/g)=[ln (V1/V2)]/V3

In above-mentioned formula, V1 represents the solvent viscosity using Ubbelohde type viscosimeter measure, and V1 and V2 are by polymer solution and molten The time for the capillary that agent (n-methyl-2-pyrrolidone) passes through viscosity tube is obtained.In addition, V3 is polymer concentration (g/ dl)。

<Non-nitrogen series solvent dissolubility>

Evaluated by operations described below：When makrolon imide resin (A) polymerize, the middle addition into reaction vessel (a) component, (b) component, (c) component and gamma-butyrolacton and heat up, at the time of internal temperature reaches 100 DEG C, raw material ((a) into Divide, (b) component, (c) component) whether dissolve.

(evaluation)

○：It is completely dissolved

△：Slightly there is dissolving residual

×：It is almost insoluble

Into makrolon imide resin (A), addition filler (C), is diluted with gamma-butyrolacton, obtains makrolon Imide resin composition.Curing accelerator (D), defoamer, levelling agent are added into the solution.The solution is slightly mixed Refining, is then repeated 3 mixings, so as to obtain being uniformly dispersed the paste of filler using high speed three roller mill.To the paste Middle blending epoxy (B), obtains makrolon imide resin paste.

Stacked film has used commercially available polyimides basement membrane, trade name VELOFLEX (registration mark), and (strain formula is spun by Japan Commercial firm's system), trade name S ' PERFLEX (Sumitomo Metal Mining Co., Ltd's system).

Double-deck CCL (trade name VELOFLEX (registration mark), the copper of Co., Ltd.'s manufacture are being spun by Japan using subtractive process 18 μm of paper tinsel, 20 μm of base material) on obtained copper circuit (L/S=50/50), using SUS halftones (MURAKAMI CO., LTD. systems, 150mesh, emulsion thickness are 30 μm), makrolon imide resin paste is printed as with the print speed printing speed of 5cm/ seconds specific Pattern, in air atmosphere at 80 DEG C dry 6 minutes (silk-screen printing).Thereafter, it is heating and curing 90 minutes with 120 DEG C, so that Obtain being applied with the stacked film of the coating (overlay film) comprising makrolon imide resin paste.The thickness of overlay film is 15 μm. The COF manufactured using Sumitomo Metal Mining Co., Ltd is with CCL's (trade name S ' PERFLEX, 8 μm of layers of copper, 12.5 μm of base material) In the case of, also using the copper circuit (L/S=16/16) obtained by subtractive process, stacked film is obtained as described above.

Using Brookfield BH type rotation viscometers, it is measured as steps described below.To wide-mouth type shading bottle Input makrolon imide resin paste 90ml, is adjusted liquid temperature to 25 DEG C ± 0.5 DEG C using Water Tank with Temp.-controlled in (100ml). Then, last 12~15 seconds using glass bar to stir 40 times, then specific rotor is set, stand after five minutes, revolved with 10rpm Turn 3 minutes, read scale at this time, calculate viscosity.Similarly, by following formula by the value of the viscosity measured under 25 DEG C, 1rpm To calculate.

Thixotropic index=viscosity (1rpm)/viscosity (10rpm)

Gained stacked film is cut into 10cm × 10cm.By 25 DEG C, 65%RH relative humidities 24 it is small when after sample with downward The state of protrusion is positioned on horizontal glass plate, evaluates the height average of corner.

(judgement)

○：Highly it is less than 2mm

△：Highly for 2mm less than 10mm

×：Highly it is more than 10mm

According to JIS-C-6471 (1995), gained stacked film is evaluated.Load-carrying is set to 300g, and the diameter of plug is set to 0.38mm, is confirmed whether to crack, bending times when record cracks.

(judgement)

◎：Do not cracked during bending more than 250 times

○：Do not cracked during bending more than 200 times

×：Cracked during less than 200 times

Tensile modulus of elasticity, elongation at break using cupping machine (trade name " Compression and Expansion testing machine TG-2kN ", Minebea Co., Ltd.s manufacture), evaluated according to JIS-K-7161 (2014).Using following conditions, to making makrolon Membranaceous sample obtained from imide resin paste cures 90 minutes at 120 DEG C is measured.

Sample size：Width 10mm × length 40mm

Draw speed：20mm/ minutes

The synthesis (b-1) of the acid dianhydride with polycarbonate backbone shown in (Production Example 1) (b) general formula (4)

Trimellitic anhydride (TMA) 167g (0.87 mole) and thionyl chloride is put into reaction vessel, make its reaction so as to Synthesize Trimellitic Anhydride Chloride.Then, Trimellitic Anhydride Chloride 183g (0.87 mole) is made and as diol compound DURANOL T5651 (the polycarbonate glycol of Asahi Chemical Corp's manufacture：1,5-PD/1,6- hexylene glycol, molecule Measure and be esterified for 1000) 434g (0.43 mole) in toluene at 30 DEG C, so as to synthesize containing polycarbonate backbone Tetracarboxylic dianhydride.

(Production Example 2)

(b-1) component 60.0g (0.04 mole), trimellitic anhydride (TMA) 3.8g (0.02 synthesized in input Production Example 1 Mole), double dehydration trimellitate (TMEG) 16.4g (0.04 mole) of ethylene glycol, the o-tolidine as diisocyanate Diisocyanate (TODI) 26.4g (0.1 mole), 1,8- diazabicyclos [5,4,0] -7-, 11 carbon as polymerization catalyst Alkene 0.08g, is dissolved in gamma-butyrolacton 97.9g.Thereafter, while stirring, while making at 80 DEG C~190 DEG C under stream of nitrogen gas Reaction 6 it is small when after, addition gamma-butyrolacton 83.9g is diluted, untill being cooled to room temperature, so as to obtain nonvolatile component and be The makrolon imide resin solution A -1 of the brown viscous of 35 mass %.

(Production Example 3)

Input Production Example 1 in synthesize (b-1) component 75.0g (0.05 mole), trimellitic anhydride 3.8g (0.02 mole), The double dehydration trimellitate 12.3g (0.03 mole) of ethylene glycol, the o-tolidine diisocyanate as diisocyanate (TODI) 26.4g (0.1 mole), 1,8- diazabicyclos [5,4,0] -7- endecatylenes 0.08g as polymerization catalyst, it is molten Solution is in gamma-butyrolacton 108.8g.Thereafter, under stream of nitrogen gas while stir, while in 80 DEG C~190 DEG C be allowed to react 6 it is small when Afterwards, addition gamma-butyrolacton 93.3g is diluted, untill being cooled to room temperature, so that it is the brown of 35 mass % to obtain nonvolatile component The sticky makrolon imide resin solution A -2 of color.

(Production Example 4)

Input Production Example 1 in synthesize (b-1) component 90.0g (0.06 mole), trimellitic anhydride 3.8g (0.02 mole), The double dehydration trimellitate 8.2g (0.02 mole) of ethylene glycol, the o-tolidine diisocyanate as diisocyanate (TODI) 26.4g (0.1 mole), 1,8- diazabicyclos [5,4,0] -7- endecatylenes 0.08g as polymerization catalyst, it is molten Solution is in gamma-butyrolacton 119.7g.Thereafter, under stream of nitrogen gas while stir, while in 80 DEG C~190 DEG C be allowed to react 6 it is small when Afterwards, addition gamma-butyrolacton 102.6g is diluted, untill being cooled to room temperature, so that it is 35 mass %'s to obtain nonvolatile component The makrolon imide resin solution A -3 of brown viscous.

(Production Example 5)

Input Production Example 1 in synthesize (b-1) component 60.0g (0.04 mole), trimellitic anhydride 3.8g (0.02 mole), The double dehydration trimellitate 16.4g (0.04 mole) of ethylene glycol, the o-tolidine diisocyanate as diisocyanate (TODI) 21.1g (0.08 mole), 2,4- toluene di-isocyanate(TDI)s (TDI) 3.5g (0.02 mole), as polymerization catalyst 1,8- diazabicyclo [5,4,0] -7- endecatylene 0.08g, are dissolved in gamma-butyrolacton 96.1g.Thereafter, under stream of nitrogen gas While stirring, while in 80 DEG C~190 DEG C be allowed to react 6 it is small when after, addition gamma-butyrolacton 82.4g is diluted, and is cooled to room Untill temperature, so as to obtain the makrolon imide resin solution A -4 for the brown viscous that nonvolatile component is 35 mass %.

(Production Example 6)

Input Production Example 1 in synthesize (b-1) component 75.0g (0.05 mole), trimellitic anhydride 3.8g (0.02 mole), The double dehydration trimellitate 12.3g (0.03 mole) of ethylene glycol, the o-tolidine diisocyanate as diisocyanate (TODI) 21.1g (0.08 mole), 2,4- toluene di-isocyanate(TDI)s (TDI) 3.5g (0.02 mole), as polymerization catalyst 1,8- diazabicyclo [5,4,0] -7- endecatylene 0.08g, are dissolved in gamma-butyrolacton 107.0g.Thereafter, under stream of nitrogen gas While stirring, while in 80 DEG C~190 DEG C be allowed to react 6 it is small when after, addition gamma-butyrolacton 91.7g is diluted, and is cooled to room Untill temperature, so as to obtain the makrolon imide resin solution A -5 for the brown viscous that nonvolatile component is 35 mass %.

(Production Example 7)

(b-1) component 75.0g (0.05 mole), trimellitic anhydride (TMA) 3.8g (0.02 synthesized in input Production Example 1 Mole), double dehydration trimellitate (TMEG) 12.3g (0.03 mole) of ethylene glycol, the o-tolidine as diisocyanate Diisocyanate (TODI) 22.5g (0.09 mole), 1,8- diazabicyclos [5,4,0] -7- 11 as polymerization catalyst Carbene 0.06g, is dissolved in gamma-butyrolacton 83.4g.Thereafter, while stirring, while making in 80 DEG C~190 DEG C under stream of nitrogen gas Reaction 6 it is small when after, addition gamma-butyrolacton 22.8g is diluted, untill being cooled to room temperature, so as to obtain nonvolatile component and be The makrolon imide resin solution A -6 of the brown viscous of 50 mass %.

(embodiment 1)

Relative to 100 mass parts of nonvolatile component of the makrolon imide resin solution A -1 obtained in Production Example 2, Add AEROSIL 300 (Japanese AEROSIL companies manufacture) 4.0 mass parts as filler, the U-CAT as curing accelerator SA1 (San-Apro Ltd. manufactures) 1.0 mass parts, BYK-054 (manufacture of BYK-Chemie companies) 1.1 matter as defoamer Part, BYK-354 (manufacture of BYK-Chemie companies) 1.2 mass parts as levelling agent are measured, obtain makrolon imide resin Composition.Said composition is slightly kneaded first, then, 3 mixings are repeated using high speed three roller mill, so as to obtain It is even to be dispersed with filler and there is thixotropic paste.Relative to 100 mass parts of paste, addition jER 157S70 (Mitsubishi Chemicals Trade name, the epoxy equivalent of phenol novolak type epoxy of Co., Ltd.'s manufacture is about 208g/eq) gamma-butyrolacton solution (solid constituent 70%) 4.0 mass parts (being 8.2 mass parts relative to 100 mass parts of makrolon imide resin (A-1)), So as to obtain the makrolon imide resin paste (1) of the present invention.Viscosity is have adjusted with gamma-butyrolacton, as a result solution viscosity For 232 pools, thixotropic index 1.32.Double-deck CCL (the trade name VELOFLEX of Co., Ltd.'s manufacture are being spun by Japan using subtractive process 18 μm of (registration mark), copper foil, 20 μm of base material) on obtained copper circuit (L/S=50/50), utilize SUS halftones (MURAKAMI CO., LTD. systems, 150mesh, emulsion thickness are 30 μm), with the print speed printing speed of 5cm/ second by makrolon acid imide of the invention Resin paste (1) is printed as specific pattern, 6 minutes dry at 80 DEG C in air atmosphere.Thereafter, it is heating and curing with 120 DEG C 90 minutes, so as to obtain being applied with COF substrates (the evaluation sample of the coating (overlay film) comprising makrolon imide resin paste Product 1).The thickness of overlay film is 15 μm.Will be evaluation result is shown in table 1.

(embodiment 2~5,7)

The material that makrolon imide resin (A) solution and (B)~(C) component are recorded using table 1, in addition, with After embodiment 1 is prepared as paste, evaluation sample 2~5,7 is made.Will be evaluation result is shown in table 1.

(embodiment 6)

Makrolon imide series resin solution (A) solution obtained in Production Example 2 and (B)~(C) components use table 1 material recorded, in addition, after preparing paste similarly to Example 1, is utilizing subtractive process by Sumitomo Metal Industries' mine strain formula The copper circuit that the COF of commercial firm's manufacture is obtained with CCL (trade name S ' PERFLEX (registration mark), 8 μm of layers of copper, 12.5 μm of base material) (L/S=16/16) on, using SUS halftones (MURAKAMI CO., LTD. systems, 150mesh, emulsion thickness are 30 μm), with 5cm/ The makrolon imide series Resin paste of the present invention is printed as specific pattern by the print speed printing speed of second, in 80 in air atmosphere It is 6 minutes dry at DEG C.Thereafter, it is heating and curing 90 minutes with 120 DEG C, so as to obtain being applied with comprising makrolon imide series tree The COF substrates (evaluation sample 6) of the coating (overlay film) of fat paste.The thickness of overlay film is 15 μm.Will be evaluation result is shown in table 1.

(comparative example 1)

Input Production Example 1 in synthesize (b-1) component 45.0g (0.03 mole), trimellitic anhydride 3.8g (0.02 mole), The double dehydration trimellitate 20.6g (0.05 mole) of ethylene glycol, the o-tolidine diisocyanate as diisocyanate (TODI) 26.4g (0.1 mole), 1,8- diazabicyclos [5,4,0] -7- endecatylenes 0.08g as polymerization catalyst, it is molten Solution is in gamma-butyrolacton 87.0g.Thereafter, under stream of nitrogen gas while stir, while after when reaction 6 is small at 80 DEG C~190 DEG C, Addition gamma-butyrolacton 74.6g is diluted, untill being cooled to room temperature, so as to obtain the brown that nonvolatile component is 35 mass % Sticky makrolon imide resin solution B -1.After operatively preparing paste similarly to Example 1, evaluation sample is made.Will Evaluation result is shown in table 1.At this time, the copolymerization amount as (b-1) component of flexible component is few, therefore warpage becomes larger.

(comparative example 2)

(b-1) the component 105.0g (0.07 mole) synthesized is put into Production Example 1, (0.02 rubs trimellitic anhydride 3.8g You), the double dehydration trimellitate 4.1g (0.01 mole) of ethylene glycol, the o-tolidine diisocyanate as diisocyanate (TODI) 21.1g (0.08 mole), 2,4- toluene di-isocyanate(TDI)s (TDI) 3.5g (0.02 mole), as polymerization catalyst 1,8- diazabicyclo [5,4,0] -7- endecatylene 0.08g, are dissolved in gamma-butyrolacton 128.8g.Thereafter, under stream of nitrogen gas While stirring, while after when reaction 6 is small at 80 DEG C~190 DEG C, addition gamma-butyrolacton 110.4g is diluted, and is cooled to room Untill temperature, so as to obtain the makrolon imide resin solution B -2 for the brown viscous that nonvolatile component is 35 mass %.With reality Apply after example 1 equally operatively prepares paste, make evaluation sample.Will be evaluation result is shown in table 1.At this time, as flexible component (b-1) component copolymerization amount it is more, therefore amount of warpage is few, but since the tensile modulus of elasticity of film is low, resist bending is presented Property difference result.

(comparative example 3)

Input Production Example 1 in synthesize (b-1) component 75.0g (0.05 mole), trimellitic anhydride 3.8g (0.02 mole), The double dehydration trimellitate 12.3g (0.03 mole) of ethylene glycol, the o-tolidine diisocyanate as diisocyanate (TODI) 13.2g (0.05 mole), 2,4- toluene di-isocyanate(TDI)s (TDI) 8.7g (0.05 mole), as polymerization catalyst 1,8- diazabicyclo [5,4,0] -7- endecatylene 0.08g, are dissolved in gamma-butyrolacton 104.3g.Thereafter, under stream of nitrogen gas While stirring, while after when reaction 6 is small at 80 DEG C~190 DEG C, addition gamma-butyrolacton 89.4g is diluted, and is cooled to room temperature Untill, so as to obtain the makrolon imide resin solution B -3 for the brown viscous that nonvolatile component is 35 mass %.With implementation After example 1 equally operatively prepares paste, evaluation sample is made.Will be evaluation result is shown in table 1.At this time, amount of warpage is few, but fracture is stretched Long rate is small, therefore the result of resistance to bend(ing) difference is presented.

(comparative example 4)

Input Production Example 1 in synthesize (b-1) component 75.0g (0.05 mole), trimellitic anhydride 9.6g (0.05 mole), O-tolidine diisocyanate (TODI) 26.4g (0.1 mole) as diisocyanate, 1,8- as polymerization catalyst Diazabicyclo [5,4,0] -7- endecatylene 0.08g, are dissolved in gamma-butyrolacton 102.2g.Thereafter, under stream of nitrogen gas on one side Stirring, while be warming up to 80 DEG C~190 DEG C, but occurs insoluble, therefore can not evaluate in polymerization process.

[table 1]

Industrial applicability

Formed by the obtained makrolon imide resin of the present invention and being had concurrently using its obtained paste as overlay film Excellent heat resistance, flexibility and the resistance to bend(ing) of material.Therefore, the various electronic component-use top coats oil as COF substrates etc. Ink, solder mask are useful, in addition, can be led as coating, smears, bonding agent etc. in the extensive of electronic equipment Used in domain, therefore can expect to be clearly helpful for industrial circle.

Claims

1. a kind of makrolon imide resin (A), it is characterised in that contain：Constituent, general formula (2) shown in general formula (1) Constituent shown in shown constituent and formula (3), when whole constituents are set to 200 moles of %, general formula (1) Shown constituent is 10 moles of more than %, and the constituent shown in general formula (2) is more than 30 moles of % and is less than 70 moles of %, And more than 50 moles % of the constituent shown in formula (3),

In general formula (1), A is the straight-chain alkyl-sub of the optionally substituent with carbon number 1~10,

In general formula (2), multiple R represent the divalent organic group of carbon number more than 1 independently of one another, and n is more than 1 integer,

A kind of 2. makrolon imide resin (A), it is characterised in that with the double dehydration trimellitate of (a) aklylene glycol, (b) acid dianhydride and (c) o-tolidine diisocyanate (TODI) work with polycarbonate backbone shown in general formula (4) For necessary copolymer composition, by all acid into when being divided into 100 moles of %, (a) aklylene glycol pair is dehydrated trimellitates and is 10 moles of more than %, the acid dianhydride with polycarbonate backbone shown in (b) general formula (4) rub more than 30 moles of % and less than 70 Your %, also, when whole amine components are set to 100 moles of %, (c) o-tolidine diisocyanate (TODI) rubs more than 50 You are %,

In general formula (4), multiple R represent the divalent organic group of carbon number more than 1 independently of one another, and n is more than 1 integer.

3. a kind of makrolon imide resin paste, it is characterised in that contain：Makrolon acyl described in claim 1 or 2 Imide resin (A), every 1 molecule have the epoxy resin (B) and filler (C) of more than 2 epoxy groups.

4. makrolon imide resin paste according to claim 3, wherein, thixotropic index is more than 1.2.

5. the makrolon imide resin paste according to claim 3 or 4, it is used for COF (chip on film).

6. a kind of electronic unit, it, which has, consolidates the makrolon imide resin paste any one of claim 3~5 Solder mask layer, sealer or adhesive linkage obtained by change.