CN106432725A - Polyamide-imide resin and manufacturing method thereof, thermosetting resin composition and cured product thereof - Google Patents
Polyamide-imide resin and manufacturing method thereof, thermosetting resin composition and cured product thereof Download PDFInfo
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- CN106432725A CN106432725A CN201610626304.8A CN201610626304A CN106432725A CN 106432725 A CN106432725 A CN 106432725A CN 201610626304 A CN201610626304 A CN 201610626304A CN 106432725 A CN106432725 A CN 106432725A
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- polyamide
- acid
- imide
- imide resin
- resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention provides a polyamide-imide resin, which has suitable alkali-solubility and can be used as the component capable of forming cured thermosetting resin compositions with excellent dielectric characteristics. The polyamide-imide resin of the invention is characterized in that, having the following general formula (1) and the structure of the following general formula (2) shown in the structure: X1 is a residue of an aliphatic diamine (a) from dimerized acid with 24 to 48 carbon atoms, X2 is a residue of an aromatic diamine (b) having a carboxyl group, and Y is each independently a cyclohexane ring or an aromatic ring.
Description
Technical field
The present invention relates to the manufacture method of a kind of polyamide-imide resin and this polyamide-imide resin and heat are hard
The property changed resin combination and the hardening thing of this thermosetting resin composition.
Background technology
A kind of resin material is all being sought in various fields based on Electrical and Electronic industry, and this resin material is with respect to alkali
The dissolubility of property solution is excellent, and can act as insulating materials, bonding agent, film raw material resin etc..
As the material that disclosure satisfy that such requirement, Patent Document 1 discloses a kind of photosensitive polymer combination, its
It is characterised by, comprises at least A agent and B agent, described A agent contains (a1) and has carboxyl and the compound of photonasty group, described B agent
Contain (b1) epoxy resin and (b2) oxime ester system Photoepolymerizationinitiater initiater, and, the feature of described photosensitive polymer combination exists
In described (b1) epoxy resin, in B agent, exists in solid form in room temperature (25 DEG C).(a1) tool in this document
There are carboxyl and the compound of photonasty group, be that at least one in the group being formed selected from following compounds has carboxyl
And the compound of photonasty group：Epoxy acrylate, urethane acrylate and acrylated acrylate.
In recent years, alkali soluble resins proposed requirement is improved constantly, especially require to improve mechanical property or heat-resisting
Property.As the resin of the epoxy acrylate system disclosed in patent document 1 or urethane acrylate system, then being difficult to meet this will
Ask.
With regard to this point, Patent Document 2 discloses a kind of alkali soluble resins it is characterised in that Tg is more than 200 DEG C,
It is within 10 points with respect to the dissolution time of 5 weight % sodium hydrate aqueous solutions, the light transmittance of 350nm is more than 5%.Patent
Polyamide-imide resin disclosed in document 2, disclosure satisfy that the requirement of described raising mechanical property or heat resistance.
Prior art document
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2012-98470 publication.
Patent document 2：Japanese Unexamined Patent Publication 2002-88154 publication.
Content of the invention
(inventing problem to be solved)
But, from the viewpoint of alkali solubility, the polyamide-imide resin disclosed in patent document 2 has asks as follows
Topic.That is, it is conventional containing resins such as epoxy acrylate or urethane acrylates as disclosed in patent document 1
Alkali soluble resins, just have sufficiently with respect to the weak alkaline aqueous solution of this degree of the aqueous sodium carbonate of 1.0 mass %
Dissolubility.And in contrast, polyamide-imide resin disclosed in patent document 2 is then as shown that in embodiment
Sample, needs to be used as developer solution using the such strong alkaline aqueous solution of sodium hydrate aqueous solution of 5 mass %.
So if it is desired to distinguishing alkali soluble resins and the patent document 2 using prior art according to product or purposes
Disclosed in alkali soluble resins, then be required for every time carrying out for developer solution being replaced with strong alkaline aqueous solution from weak alkaline aqueous solution
Or contrary replacement operation, lead to productivity to significantly reduce.In addition, developer solution to be replaced with strong basicity from weak alkaline aqueous solution water-soluble
After liquid, originally the wastewater treatment of reply weak alkaline aqueous solution also must be altered to also cope with strong alkaline aqueous solution.This gives up
The change of water process it is possible to the reduction of industrial productivity can be led to, for example, needs huge equipment investment, operating cost to improve
Deng.
Therefore, from the viewpoint guaranteeing industrial productivity to consider it is desirable to alkali soluble resins as usual, in 1.0 weights
In the such weak alkaline aqueous solution of aqueous sodium carbonate of amount %, there is sufficient dissolubility.
In addition, applying in the case of Electrical and Electronic industrial field, the combination of the hardening resin containing alkali soluble resins
The hardening thing of thing preferably dielectric property excellent (specifically can illustrate dielectric constant is low or dielectric absorption is low).
It is an object of the invention to provide the manufacturer of a kind of polyamide-imide resin and this polyamide-imide resin
Method, described polyamide-imide resin be used the aqueous sodium carbonate of 1.0 mass % as alkaline solution in the case of also can
Enough dissolve that is to say, that having suitable alkali solubility, and can be used as the heat that can form the excellent hardening thing of dielectric property
The composition of curable resin composition.In addition, it is an object of the invention to provide a kind of thermosetting resin composition and hardening
Thing, described thermosetting resin composition contains described polyamide-imide resin, and described hardening thing is to make this thermosetting
Resin combination hardens and obtains.
(technological means of solve problem)
The present invention providing to solve described problem is as described below.
[1] a kind of polyamide-imide resin is it is characterised in that have the structure shown in following formulas (1) and following logical
Structure shown in formula (2).
X1It is the residue of the aliphatic diamine (a) of dimeric dibasic acid being 24 to 48 from carbon number, X2It is the aromatic series with carboxyl
The residue of diamines (b), Y is separately cyclohexane ring or aromatic rings.
[2] polyamide-imide resin according to described [1] is it is characterised in that acid number is more than 30mgKOH/g.
[3] polyamide-imide resin according to described [1] or [2] it is characterised in that described from carbon number be 24
Containing ratio to the aliphatic diamine (a) of 48 dimeric dibasic acid is 20 weight % to 60 weight %.
[4] polyamide-imide resin according to any one of described [1] is to [3] is it is characterised in that described formula
(1), in the cyclohexane ring being represented with Y and in described formula (2) and/or aromatic rings, the content of cyclohexane ring is with respect to aromatic rings
The mol ratio of content is 85/15 to 100/0.
[5] polyamide-imide resin according to any one of described [1] is to [4] is it is characterised in that described have
The aromatic diamine (b) of carboxyl comprises selected from 3,5- diaminobenzoic acid and 5,5'- di-2-ethylhexylphosphine oxide ortho-aminobenzoic acid institute group
In the group becoming more than a kind.
[6] a kind of thermosetting resin composition is it is characterised in that contain with good grounds described [1] to any one of [5]
Polyamide-imide resin and thermal sclerosing material.
[7] thermosetting resin composition according to described [6] is it is characterised in that described thermal sclerosing material is
Epoxy resin.
[8] thermosetting resin composition according to described [6] or [7] promotees it is characterised in that also containing thermmohardening
Enter agent.
[9] a kind of hardening thing is it is characterised in that be the thermosetting resin according to any one of described [6] are to [8]
The hardening thing of composition.
[10] a kind of manufacture method of polyamide-imide resin is it is characterised in that possess：Imidation step, makes to be derived from
Carbon number be 24 to 48 dimeric dibasic acid aliphatic diamine (a), have carboxyl aromatic diamine (b) and selected from hexamethylene-
1 kind or 2 kinds in the group that 1,2,4- tricarboxylic acids -1,2- acid anhydride (c) and trimellitic anhydride (d) are formed is reacted and is obtained acyl
Imines compound (A)；And amide imide step, make the described acid imide compound (A) being obtained by described imidation step, with
Diisocyanate cpd (e) is reacted, and obtains the polyamide-imide resin shown in following formulas (3).
In described formula (3), X is separately diamines residue, and Y is separately cyclohexane ring or aromatic rings, and Z is
The residue of diisocyanate cpd (e), n is natural number.
[11] manufacture method of the polyamide-imide resin according to described [10] is it is characterised in that by described acyl
The acid number of the described polyamide-imide resin that amine imide step obtains is more than 30mgKOH/g.
[12] manufacture method of the polyamide-imide resin according to described [10] or [11] is it is characterised in that institute
State from carbon number the addition of the aliphatic diamine (a) of dimeric dibasic acid being 24 to 48, make described from carbon number be 24 to 48
The containing ratio of the aliphatic diamine (a) of dimeric dibasic acid is the amount to 60 weight % for 20 weight %.
[13] manufacture method of the polyamide-imide resin according to any one of described [10] are to [12], its feature
It is, hexamethylene -1,2,4- tricarboxylic acids -1, the usage amount of 2- acid anhydride (c) is with respect to the mol ratio of the usage amount of trimellitic anhydride (d)
It is 85/15 to 100/0.
[14] manufacture method of the polyamide-imide resin according to any one of described [10] are to [13], its feature
It is, the described aromatic diamine (b) with carboxyl comprises selected from 3,5- diaminobenzoic acid and 5,5'- di-2-ethylhexylphosphine oxide neighbour's ammonia
In the group that yl benzoic acid is formed more than a kind.
[15] manufacture method of the polyamide-imide resin according to any one of described [10] are to [14], its feature
It is, described diisocyanate cpd (e) is aliphatic isocyanates compound.
(invention effect)
According to the present invention, provide a kind of polyamide-imide resin and its manufacture method, described polyamide-imide resin
Even if it is also possible to dissolve in the case of using gentle alkaline solution as the aqueous sodium carbonate of 1.0 mass %.
In addition, according to the present invention, providing a kind of thermosetting resin composition, even if described thermosetting resin composition
It is also possible to dissolve in the case of using gentle alkaline solution as the aqueous sodium carbonate of 1.0 mass %.And then,
According to the present invention, provide a kind of hardening thing, described hardening thing is the hardening thing of described thermosetting resin composition, and has excellent
Different dielectric property.
Specific embodiment
Below, embodiments of the present invention are illustrated.
The polyamide-imide resin of one embodiment of the present invention, has the structure shown in following formulas (1) and following
Structure shown in formula (2).
Wherein, X1Be from carbon number be 24 to 48 dimeric dibasic acid aliphatic diamine (a) (in this specification also referred to as
" dimer diamines (a) ") residue.X2It is that the aromatic diamine (b) with carboxyl (is also referred to as " containing carboxyl in this specification
Diamines (b) ") residue.Y is separately hexamethylene or aromatic rings.
By comprising the structure shown in described formula (1) and the structure shown in described formula (2), alkali solubility can be formed excellent
Different polyamide-imide resin, though this polyamide-imide resin using as 1.0 mass % aqueous sodium carbonate this
It is also possible to dissolve in the case of the gentle alkaline solution of sample.In addition, comprising the thermosetting tree of this polyamide-imide resin
The hardening thing of oil/fat composition, can have excellent dielectric property.
Dimer diamines (a) can be by by the carboxyl in the dimer of the aliphatic unsaturated carboxylic acid of carbon number 12 to 24 also
Former amination and obtain.That is, from dimeric dibasic acid aliphatic diamine be dimer diamines (a) can by following manner Lai
Obtain：So that the such as unrighted acid such as oleic acid, linoleic acid is polymerized and form dimeric dibasic acid, after reducing this dimeric dibasic acid, carry out amination.
As such aliphatic diamine, for example, can use PRIAMINE 1073, PRIAMINE 1074, PRIAMINE 1075
Commercially available products such as (Croda Japan company manufacture, trade name), these commercially available products are the diamines of the skeleton with carbon number 36.Dimerization
Thing diamines (a) it is sometimes preferably that being 28 to 44 dimeric dibasic acid from carbon number, sometimes more preferably from carbon number be 32 to 40
Dimeric dibasic acid.
The specific example of carboxylic diamines (b) can be enumerated：3,5- diaminobenzoic acid, 3,4- diaminobenzoic acid,
5,5'- di-2-ethylhexylphosphine oxide (ortho-aminobenzoic acid), benzidine -3,3'- dicarboxylic acids etc..Carboxylic diamines (b) can be changed by a kind
Compound constitutes or is made up of multiple compounds.To consider, carboxylic diamines (b) is excellent from the acquired viewpoint of raw material
Choosing is containing 3,5- diaminobenzoic acid, 5,5'- di-2-ethylhexylphosphine oxide (ortho-aminobenzoic acid).
In the polyamide-imide resin of one embodiment of the present invention, the content of structure shown in described formula (1) with
The relation of the content of structure shown in described formula (2) does not have restriction.From the alkali solubility making polyamide-imide resin and
The balance comprising other characteristics such as the mechanical property of the hardening thing of the thermosetting resin composition of polyamide-imide resin is good
Good viewpoint considering, the content (unit of dimer diamines (a)：Weight %) preferably 20 weight % to 60 weight %, more
Preferably 30 weight % are to 50 weight %.In this specification, so-called " content of dimer diamines (a) ", represent and manufacture polyamides
A kind of addition of dimer diamines (a) put into as the of raw material during amine imide resin is with respect to manufactured polyamide
The ratio of the weight of imide resin.Wherein, " weight of manufactured polyamide-imide resin ", is used to manufacture polyamide
The addition of whole raw materials of imide resin, deducts the water (H generating because of imidizate2O) and because of amidatioon generate
Carbon dioxide (CO2) theoretical amount after value.
From the alkali solubility making polyamide-imide resin and the thermosetting resin group that comprises polyamide-imide resin
The good viewpoint of balance of other characteristics such as the mechanical property of the hardening thing of compound considering, one embodiment of the present invention poly-
Acid number (solid constituent acid number) preferably more than the 30mgKOH/g of amide imide resin, more preferably 30mgKOH/g with
Upper below 150mgKOH/g, particularly preferably more than 50mgKOH/g below 120mgKOH/g.
To consider from the alkali-soluble viewpoint improving polyamide-imide resin, in described formula (1) and described formula (2)
Cyclohexane ring is preferably had with the part that Y represents.From the alkali solubility making polyamide-imide resin and comprise polyamide
The viewpoint that the balance of other characteristics such as the mechanical property of the hardening thing of the thermosetting resin composition of imide resin is good is come
Consider, described with Y represent partly in aromatic rings as follows with the relation of the amount of cyclohexane ring：The content of cyclohexane ring with respect to
The mol ratio of the content of aromatic rings preferably 85/15 to 100/0, more preferably 90/10 to 99/1, more preferably 90/
10 to 98/2.
The polyamide-imide resin of one embodiment of the present invention can also have the part knot shown in following formulas (i)
Structure.
Wherein, X3Be diamines (f) beyond dimer diamines (a) and carboxylic diamines (b) (in this specification, also referred to as
Be " other diamines (f) ") residue, Y, in the same manner as described formula (1) and described formula (2), is separately aromatic rings
Or cyclohexane ring.Other diamines (f) can be made up of a kind of compound or be made up of multiple compounds.
The specific example of other diamines (f) can enumerate following aromatic diamine, i.e. 2,2- double [4- (4- aminobenzene oxygen
Base) phenyl] propane, double [4- (3- amino-benzene oxygen) phenyl] sulfone, double [4- (4- amino-benzene oxygen) phenyl] sulfone, the double [4- of 2,2-
(4- amino-benzene oxygen) phenyl] HFC-236fa, double [4- (4- amino-benzene oxygen) phenyl] methane, double (the 4- aminobenzene oxygen of 4,4'-
Base) biphenyl, double [4- (4- amino-benzene oxygen) phenyl] ether, double [4- (4- amino-benzene oxygen) phenyl] ketone, double (the 4- aminobenzene of 1,3-
Epoxide) benzene, double (4- amino-benzene oxygen) benzene of 1,4-, 2,2'- dimethyl diphenyl base -4,4'- diamines, 2,2'- be double (trifluoromethyl)
Xenyl -4,4'- diamines, 2,6,2', 6'- tetramethyl -4,4'- diamines, 5,5'- dimethyl -2,2'- sulfonyl-xenyl -4,
4'- diamines, 3,3'- dihydroxybiphenyl base -4,4'- diamines, (4,4'- diaminourea) diphenyl ether, (4,4'- diaminourea) diphenyl
Sulfone, (4,4'- diaminourea) diphenylketone, (3,3'- diaminourea) diphenylketone, (4,4'- diaminourea) diphenyl methane, (4,4'-
Diaminourea) diphenyl ether, (3,3'- diaminourea) diphenyl ether etc.；Following aliphatic diamine can also be enumerated, i.e. hexamethylene diamine, pungent two
Amine, decamethylene diamine, dodecamethylene diamine, octadecamethylene diamine, 4,4' methylene bis (cyclohexylamine), IPD, 1,4- hexamethylene two
Amine, ENB diamines etc..
The polyamide-imide resin of one embodiment of the present invention can also have the structure shown in following formulas (ii).
Wherein, Z can be fatty group or contain aromatic group.When Z is fatty group, ring can be comprised
The alcyls such as hexane ring.According to manufacture method described hereinafter, then Z is the residue of diisocyanate cpd (e).
The manufacture method of the polyamide-imide resin of one embodiment of the present invention does not have restriction.According to following
Manufacture method, can expeditiously manufacture the polyamide-imide resin of one embodiment of the present invention.
The manufacture method of the polyamide-imide resin of one embodiment of the present invention possesses imidation step and acid amides
Imidation step.
In imidation step, make dimer diamines (a), carboxylic diamines (b) and be selected from hexamethylene -1,2,
1 kind in the group that 4- tricarboxylic acids -1,2- acid anhydride (c) and trimellitic anhydride (d) are formed or 2 kinds is reacted, and obtains acid imide
Compound (A).
It is 20 weight % to 60 weights that the addition of dimer diamines (a) preferably makes the content of dimer diamines (a)
The amount of amount %, the content more preferably making dimer diamines (a) is the amount to 50 weight % for 30 weight %.Dimer diamines
A the definition of the content of () is as previously discussed.
As needed it is also possible to dimer diamines (a) and carboxylic diamines (b) in the lump using other diamines (f).
To consider from the alkali-soluble viewpoint improving polyamide-imide resin, preferably to make in imidation step
With hexamethylene -1,2,4- tricarboxylic acids -1,2- acid anhydride (c).The usage amount of hexamethylene -1,2,4- tricarboxylic acids -1,2- acid anhydride (c) is with respect to inclined
The mol ratio of the usage amount of benzenetricarboxylic anhydride (d) preferably 85/15 to 100/0, more preferably 90/10 to 99/1, more preferably
Be 90/10 to 98/2.
The diamine compound (B) being used for obtaining acid imide compound (A) (specifically refers to dimer diamines (a) and carboxylic
Diamines (b) and other diamines (f) using as needed) amount and acid anhydrides (C) (specifically refer to selected from hexamethylene -1,2,
In the group that 4- tricarboxylic acids -1,2- acid anhydride (c) and trimellitic anhydride (d) are formed a kind or 2 kinds) amount relation unlimited
Fixed.The usage amount of acid anhydrides (C) preferably with respect to the molar ratio of the usage amount of diamine compound (B) be more than 2.0 2.4 with
Under amount, be more preferably the amount that this molar ratio is less than more than 2.0 2.2.
Diamine compound (B) and acid anhydrides (C) is made to be reacted unlimited with the reaction temperature obtaining acid imide compound (A)
Fixed.In general, it is preferred to be in the range of 120 DEG C to 200 DEG C, more preferably in the range of 140 DEG C to 180 DEG C.
The reaction dissolvent being used for obtaining acid imide compound (A) does not have restriction.As the specific example of this reaction dissolvent, can
To enumerate：Gamma-butyrolacton, cyclohexanone, dimethylacetylamide (DMAC), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N- first
Base -2-Pyrrolidone (NMP), sulfolane, cyclopentanone, diethylene glycol dimethyl ether (diglyme), triglyme (triglyme)
Deng.The reaction dissolvent being used for obtaining acid imide compound (A) can be made up of a kind of compound, it is possible to use two or more chemical combination
The combination of thing is used as reaction dissolvent.Wherein, because the step generating acid imide compound (A) needs high reaction temperature, so
Preferably with formed selected from gamma-butyrolacton, cyclohexanone, triglyme, diethylene glycol dimethyl ether and cyclopentanone
One kind or two or more in group, it is used as the reaction dissolvent for obtaining acid imide compound (A), the boiling point of these reaction dissolvents
Height, the dissolubility of the polymer being obtained is relatively good, and using not needing strict moisture management during polymer solution.
Due to water can be generated in imidization reaction, so carrying out for during the reaction obtaining acid imide compound (A), preferably
Be exist can with imidization reaction in generate water azeotropic aromatic hydrocarbon.As such aromatic hydrocarbon, for example may be used
To enumerate：Benzene,toluene,xylene, ethylbenzene, mesitylene etc..Wherein, from toxicity is relatively low and low boiling point thus easy distillation are gone
From the aspect of removing, preferably toluene.
In amide imide step, make the acid imide compound (A) being obtained by described imidation step, with two isocyanic acids
Ester compounds (e) are reacted and are obtained polyamide-imide resin, and described polyamide-imide resin comprises there is following leading to
The material of the structure shown in formula (3).
The concrete species of diisocyanate cpd (e) does not have restriction.Diisocyanate cpd (e) can be by 1
Plant compound to constitute or be made up of multiple compounds.
The specific example of diisocyanate cpd (e) can be enumerated：4,4'- methyl diphenylene diisocyanate, 2,4-
Toluene di-isocyanate(TDI), 2,6- toluene di-isocyanate(TDI), 1,5- naphthalene diisocyanate, O-phthalic group diisocyanate, isophthalic
The aromatic diisocyanates such as diformazan group diisocyanate, 2,4- toluene support dimer；Hexamethylene diisocyanate, trimethyl
Hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, IPDI, ENB two isocyanic acid
Aliphatic diisocyanates such as ester etc..From making the alkali solubility of polyamide-imide resin and the printing opacity of polyamide-imide resin
Considering, preferably diisocyanate cpd (e) contains aliphatic isocyanates to all good viewpoint of property, more preferably
Diisocyanate cpd (e) is exactly aliphatic isocyanates.
In amide imide step, the usage amount of diisocyanate cpd (e) does not have and limits.From making polyamide acyl
Imide resin has appropriate alkali-soluble viewpoint to consider, the usage amount of diisocyanate cpd (e) is as follows：According to relatively
In in order to obtain imide compound (A) and using the molar ratio of amount of diamine compound (B) count, preferably 0.3
Above less than 1.0, more preferably less than more than 0.4 0.95, particularly preferably less than more than 0.50 0.90.
In amide imide step, the reaction temperature of amide imideization reaction does not have and limits.Lift an acid amides acyl sub-
For the specific example of the reaction temperature of aminating reaction, it is less than more than 130 DEG C 200 DEG C of scope, sometimes it is also preferred that at 150 DEG C
Reacted in above less than 180 DEG C of scope.
In amide imideization reaction in amide imide step, can be as needed using catalyst.Can make
The specific example of catalyst can be enumerated：The amines such as triethylamine, lutidines, picoline, triethylenediamine；First
The alkali metal such as lithium alkoxide, sodium methoxide, lithium ethoxide, caustic alcohol, magnesium ethylate, butanol potassium, potassium fluoride, sodium fluoride or the chemical combination of alkaline-earth metal
Thing；The metals such as cobalt, titanium, tin, zinc or semimetallic compound etc..
Using the polyamide-imide resin manufactured by above manufacture method, comprise to have shown in following formulas (3)
The material of structure.
In described formula (3), X is separately diamines residue (residue of diamine compound (B)), and Y is separately
It is aromatic rings or cyclohexane ring, Z is the residue of diisocyanate cpd (e).N is natural number.
Contain carboxyl using the polyamide-imide resin manufactured by above manufacture method.From raising polyamidoimide
The alkali-soluble viewpoint of resin considering, acid number preferably more than 50mgKOH/g.From the alkali improving polyamide-imide resin
Considering, the upper limit of described acid number does not have and limits the viewpoint of dissolubility.From so that comprising the thermmohardening of polyamide-imide resin
Other characteristics such as the mechanical property of hardening thing of property resin combination are good with the alkali-soluble balance of polyamide-imide resin
Viewpoint considering, described acid number preferably below 150mgKOH/g, more preferably below 120mgKOH/g.
Below, thermosetting resin composition is illustrated, described thermosetting resin composition employs the present invention
An embodiment polyamide-imide resin.Because the polyamide-imide resin of one embodiment of the present invention has carboxylic
Base, so by using suitable thermal sclerosing material, just can carry out polymerisation (hardening using this carboxyl as reactive site
Reaction).Therefore, the thermosetting resin composition of one embodiment of the present invention, poly- containing one embodiment of the present invention
Amide imide resin and thermal sclerosing material.This thermal sclerosing material can be made up of or by multiple a kind of material
Material is constituted.
Thermal sclerosing material is that can be had with the polyamide-imide resin of one embodiment of the present invention using heat
The material that some carboxyls are reacted.This material can illustrate：The compound with epoxy radicals is, the change with NCO
Compound etc..Any one compound all preferably have multiple can be (also referred to as " anti-in this specification with the functional group of carboxyl reaction
Answering property functional group ").
As one of the compound with epoxy radicals, epoxy resin can be enumerated.As epoxy resin, for example, can lift
Go out：The bisphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin；Phenol novolac is clear
The phenolic resin varnish type epoxy resins such as paint epoxy resin, cresol novolac epoxy, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin；
Bicyclopentadiene and phenols react the epoxides of obtained dicyclopentadiene-type phenol resin；2,2', 6,6'- tetramethyl biphenyl
The biphenyl type epoxy resins such as the epoxides of phenol；The fragrance such as the epoxy resin with naphthalene skeleton, the epoxy resin with fluorene skeleton
Family epoxy resin or the hydride of these fragrant family epoxy resin；Ethylene glycol diglycidylether, diethylene glycol diglycidyl
The aliphatic epoxy resins such as glycerin ether, neopentylglycol diglycidyl ether, 1,6 hexanediol diglycidylether；3,4- epoxide ring
The alicyclic epoxy resins such as double (3,4- epoxycyclohexyl) ester of hexyl formic acid -3,4- epoxycyclohexanecarboxylate, adipic acid；Isocyanide is urinated
Sour three-glycidyl ester etc. contains epoxy resin of heterocycle etc..
Special from the heat resistance of the hardening thing of the thermosetting resin composition improving one embodiment of the present invention and machinery
The viewpoint of property considering, in the case that thermal sclerosing material contains epoxy resin, preferably contain bisphenol-type epoxy resin and
At least one in biphenyl type epoxy resin.
In the thermosetting resin composition of one embodiment of the present invention the amount of contained polyamide-imide resin with
The relation of the amount of the thermal sclerosing materials such as epoxy resin does not have restriction.From the thermosetting improving one embodiment of the present invention
The viewpoint of the mechanical property of the hardening thing of resin combination, heat resistance etc. considering, the epoxide equivalent isoreactivity of epoxy resin
Functional equivalent (can calculate according to the acid number of polyamide-imide resin with respect to the carboxyl equivalent of polyamide-imide resin
Ratio out) preferably less than more than 0.6 1.3, more preferably less than more than 0.8 1.2.
The thermosetting resin composition of one embodiment of the present invention can also contain hardening accelerator.That is,
The thermosetting resin composition of one embodiment of the present invention can the Asia of the polyamide acyl containing one embodiment of the present invention
Polyimide resin, epoxy resin and hardening accelerator.
When the thermosetting resin composition of one embodiment of the present invention contains hardening accelerator, the kind of hardening accelerator
Class does not have restriction.Hardening accelerator can be made up of a kind of material or be made up of many kinds of substance.
It is that in case of the material promoting thermmohardening, hardening accelerator can be enumerated by hardening accelerator：Tertiary amine chemical combination
Thing, quaternary ammonium salt, imidazoles, phosphine compound, salt (phosphonium salt) etc..More specifically, can enumerate：Three second
Amine, triethylenediamine, benzyl dimethylamine, 2,4,6- tri- (dimethylaminomethyl) phenol, 1,8- diaza-bicyclo (5,4,0) ten
One alkene -7 grade tertiary amine compound；2-methylimidazole, 2,4- methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole, 2-
The imidazoles such as phenyl -4-methylimidazole；The phosphines such as triphenylphosphine, tributylphosphine, three (p-methylphenyl) phosphine, three (nonyl phenyl) phosphine
Compound；The salt such as tetraphenylboronic acid tetraphenyl, tetraphenyl four naphthoic acid borate；Triphenyl phenates
The glycine betaine shape organophosphor chemical combination such as product of (triphenylphosphonio phenolate), benzoquinones and triphenylphosphine
Thing etc..
In the case that the thermosetting resin composition of one embodiment of the present invention contains thermal sclerosing material, by inciting somebody to action
The thermosetting resin composition of one embodiment of the present invention is heated, and this thermosetting resin composition can be made hard
Change.The curing conditions such as hardening temperature, firm time can be according to contained composition in thermosetting resin composition come suitably
Set.As one of curing condition, can enumerate：Hardening temperature is set as less than more than 80 DEG C 300 DEG C, and firm time sets
For 30 minutes to 6 hours.
The implementation described above is the record made for ease of understanding the present invention, is not intended to limit this
Bright and record.Therefore, the objective of each key element disclosed in described embodiment is institute in the technical scope also comprise the present invention
The whole design alteration belonging to or equipollent.
Embodiment
To further illustrate the present invention below by embodiment, but the present invention is not limited to these embodiments.
(embodiment 1)
At room temperature, in the four-hole boiling flask of the 300mL possessing nitrogen ingress pipe, thermometer, agitator, add as two
(Croda Japan company manufactures the aliphatic diamine of the dimeric dibasic acid from carbon number 36 of polymers diamines (a), ProductName
PRIAMINE1075) 28.61g (0.052mol), the 3,5- diaminobenzoic acid 4.26g as carboxylic diamines (b)
(0.028mol), gamma-butyrolacton 85.8g dissolving.
Then, hexamethylene -1,2,4- tricarboxylic acid anhydride (c) 30.12g (0.152mol), trimellitic anhydride (d) 3.07g are added
(0.016mol), keep 30 minutes in room temperature.Then add toluene 30g, be warmed up to 160 DEG C, eliminate and generate with toluene simultaneously
Water after, keep 3 hours, be cooled to room temperature afterwards, thus, obtain the solution containing acid imide compound.
To being obtained in the solution containing acid imide compound, add the trimethyl as diisocyanate cpd (e)
Hexamethylene diisocyanate 14.30g (0.068mol), keeps 32 hours in 160 DEG C of temperature, with cyclohexanone 21.4g in addition
Dilution, thus, obtains the solution containing polyamide-imide resin (A-1).The weight of the polyamide-imide resin being obtained
Amount average molecular weight Mw is 5250, and solid constituent is 41.5 mass %, and acid number is 63mgKOH/g, the content of dimer diamines (a)
It is 40.0 weight %.
(embodiment 2)
At room temperature, in the four-hole boiling flask of the 300mL possessing nitrogen ingress pipe, thermometer, agitator, add as two
(Croda Japan company manufactures the aliphatic diamine of the dimeric dibasic acid from carbon number 36 of polymers diamines (a), ProductName
PRIAMINE1075) 29.49g (0.054mol), the 3,5- diaminobenzoic acid 4.02g as carboxylic diamines (b)
(0.026mol), gamma-butyrolacton 73.5g dissolving.
Then, hexamethylene -1,2,4- tricarboxylic acid anhydride (c) 31.71g (0.160mol), trimellitic anhydride (d) 1.54g are added
(0.008mol), keep 30 minutes in room temperature.Then add toluene 30g, be warmed up to 160 DEG C, eliminate and generate with toluene simultaneously
Water after, keep 3 hours, be cooled to room temperature afterwards, thus, obtain the solution containing acid imide compound.
To being obtained in the solution containing acid imide compound, add the trimethyl as diisocyanate cpd (e)
Hexamethylene diisocyanate 6.90g (0.033mol) and dicyclohexyl methyl hydride diisocyanate 8.61g (0.033mol),
160 DEG C of temperature keeps 32 hours, is diluted with cyclohexanone 36.8g, thus, obtains containing polyamide-imide resin
Solution (A-2).Weight average molecular weight Mw of the polyamide-imide resin being obtained is 5840, and solid constituent is 40.4 matter
Amount %, acid number is 62mgKOH/g, and the content of dimer diamines (a) is 40.1 weight %.
(embodiment 3)
At room temperature, in the four-hole boiling flask of the 300mL possessing nitrogen ingress pipe, thermometer, agitator, add as two
(Croda Japan company manufactures the aliphatic diamine of the dimeric dibasic acid from carbon number 36 of polymers diamines (a), ProductName
PRIAMINE1075) 29.49g (0.054mol), the 3,5- diaminobenzoic acid 4.02g as carboxylic diamines (b)
(0.026mol), gamma-butyrolacton 75.0g dissolving.
Then, add hexamethylene -1,2,4- tricarboxylic acid anhydride (c) 33.29g (0.168mol), keep 30 minutes in room temperature.So
Add toluene 30g afterwards, be warmed up to 160 DEG C, after eliminating the water simultaneously generating with toluene, keep 3 hours, be cooled to room afterwards
Temperature, thus, obtains the solution containing acid imide compound.
To being obtained in the solution containing acid imide compound, add two hexamethylenes as diisocyanate cpd (e)
Dicyclohexylmethane diisocyanate 16.79g (0.064mol), keeps 32 hours in 160 DEG C of temperature, in addition dilute with cyclohexanone 37.5g
Release, thus, obtain the solution containing polyamide-imide resin (A-3).The weight of the polyamide-imide resin being obtained
Average molecular weight Mw is 6430, and solid constituent is 41.2 mass %, and acid number is 63mgKOH/g, and the content of dimer diamines (a) is
39.3 weight %.
(embodiment 4)
At room temperature, in the four-hole boiling flask of the 300mL possessing nitrogen ingress pipe, thermometer, agitator, add as two
(Croda Japan company manufactures the aliphatic diamine of the dimeric dibasic acid from carbon number 36 of polymers diamines (a), ProductName
PRIAMINE1075) 33.01g (0.060mol), the 5,5'- di-2-ethylhexylphosphine oxide (o-amino benzoyl as carboxylic diamines (b)
Acid) 5.73g (0.020mol), gamma-butyrolacton 95.4g dissolve.
Then, hexamethylene -1,2,4- tricarboxylic acid anhydride (c) 31.71g (0.160mol), trimellitic anhydride (d) 1.54g are added
(0.008mol), keep 30 minutes in room temperature.Then add toluene 30g, be warmed up to 160 DEG C, eliminate and generate with toluene simultaneously
Water after, keep 3 hours, be cooled to room temperature afterwards, thus, obtain the solution containing acid imide compound.
To being obtained in the solution containing acid imide compound, add the trimethyl as diisocyanate cpd (e)
Hexamethylene diisocyanate 7.40g (0.035mol) and dicyclohexyl methyl hydride diisocyanate 9.23g (0.035mol),
160 DEG C of temperature keeps 32 hours, is diluted with cyclohexanone 23.9g, thus, obtains containing polyamide-imide resin
Solution (A-4).Weight average molecular weight Mw of the polyamide-imide resin being obtained is 8310, and solid constituent is 41.3 matter
Amount %, acid number is 70mgKOH/g, and the content of dimer diamines (a) is 41.5 weight %.
(embodiment 5)
At room temperature, in the four-hole boiling flask of the 300mL possessing nitrogen ingress pipe, thermometer, agitator, add as two
(Croda Japan company manufactures the aliphatic diamine of the dimeric dibasic acid from carbon number 36 of polymers diamines (a), ProductName
PRIAMINE1075) 33.01g (0.060mol), the 5,5'- di-2-ethylhexylphosphine oxide (o-amino benzoyl as carboxylic diamines (b)
Acid) 5.73g (0.020mol), gamma-butyrolacton 96.5g dissolve.
Then, hexamethylene -1,2,4- tricarboxylic acid anhydride (c) 31.71g (0.160mol), trimellitic anhydride (d) 1.54g are added
(0.008mol), keep 30 minutes in room temperature.Then add toluene 30g, be warmed up to 160 DEG C, eliminate and generate with toluene simultaneously
Water after, keep 3 hours, be cooled to room temperature afterwards, thus, obtain the solution containing acid imide compound.
To being obtained in the solution containing acid imide compound, add the trimethyl as diisocyanate cpd (e)
Hexamethylene diisocyanate 3.70g (0.018mol) and dicyclohexyl methyl hydride diisocyanate 13.85g (0.053mol),
160 DEG C of temperature keeps 32 hours, is diluted with cyclohexanone 24.1g, thus, obtains containing polyamide-imide resin
Solution (A-5).Weight average molecular weight Mw of the polyamide-imide resin being obtained is 8900, and solid constituent is 41.0 matter
Amount %, acid number is 69mgKOH/g, and the content of dimer diamines (a) is 41.0 weight %.
(comparative example 1)
At room temperature, add 2,2'- in the four-hole boiling flask of the 300mL possessing nitrogen ingress pipe, thermometer, agitator double
[4- (4- amino-benzene oxygen) phenyl] propane 6.98g, 3,5- diaminobenzoic acid 3.80g, polyether diamine (Huntsman company system
Make, ProductName ELASTAMINE RT1000, molecular weight 1025.64) 8.21g and gamma-butyrolacton 86.49g dissolving.
Then, add hexamethylene -1,2,4- tricarboxylic acids -1,2- acid anhydride 17.84g and trimellitic anhydride 2.88g, keep in room temperature
30 minutes.Then add toluene 30g, be warmed up to 160 DEG C, after eliminating the water simultaneously generating with toluene, keep 3 hours, it
After be cooled to room temperature, thus, obtain acid imide compound solution.
Add trimellitic anhydride 9.61g and tri-methyl hexamethylene two isocyanic acid in the acid imide compound solution being obtained
Ester 17.45g, keeps 32 hours in 160 DEG C of temperature.So, obtain the polyamideimide resin solution (B- containing carboxyl
1).Solid constituent is 40.1 mass %, and acid number is 83mgKOH/g.
(comparative example 2)
At room temperature, add 3,5- bis- in the four-hole boiling flask of the 300mL possessing nitrogen ingress pipe, thermometer, agitator
(chemical industrial company of SHIN-ETSU HANTOTAI manufactures, ProductName X-22-9409, amine equivalent 680g/ for aminobenzoic acid 4.05g, modified silicone oil
Eq) 39.98g, gamma-butyrolacton 76.72g dissolve.
Then, add hexamethylene -1,2,4- tricarboxylic acid anhydride 20.11g, trimellitic anhydride 2.69g, keep 30 points in room temperature
Clock.Then add toluene 30g, be warmed up to 160 DEG C, after eliminating the water simultaneously generating with toluene, keep 3 hours, cold afterwards
But arrive room temperature, thus, obtain acid imide compound solution.
Add trimellitic anhydride 0.94g, hexamethylene -1,2,4- tricarboxylic acid anhydride in the acid imide compound solution being obtained
1.80g, dicyclohexyl methyl hydride -4,4'- diisocyanate 13.77g, keep 32 hours in 160 DEG C of temperature, thus, obtain
Polyamideimide resin solution containing carboxyl (B-2).Solid constituent is 52.0 mass %, and acid number is 65mgKOH/g.
(comparative example 3)
At room temperature, add 2,2'- in the four-hole boiling flask of the 300mL possessing nitrogen ingress pipe, thermometer, agitator double
[4- (4- amino-benzene oxygen) phenyl] propane 10.26g, 3,5- diaminobenzoic acid 3.80g, gamma-butyrolacton 79.48g simultaneously dissolves.
Then, add hexamethylene -1,2,4- tricarboxylic acid anhydride 17.84g, trimellitic anhydride 2.88g, keep 30 points in room temperature
Clock.Then add toluene 30g, be warmed up to 160 DEG C, after eliminating the water simultaneously generating with toluene, keep 3 hours, cold afterwards
But arrive room temperature, thus, obtain acid imide dicarboxylic acid solution.
To in the acid imide dicarboxylic acid solution being obtained, add trimellitic anhydride 9.61g, tri-methyl hexamethylene two isocyanide
Acid esters 17.87g, keeps 32 hours in 160 DEG C of temperature, thus, obtains the polyamideimide resin solution containing carboxyl
(B-3).Solid constituent is 40.2 mass %, and acid number is 90mgKOH/g.
(embodiment 6 to 10)
Make thermosetting resin composition (embodiment 6 to 10), described thermosetting resin composition contains：As heat
(Mitsubishi Chemical Ind manufactures the bisphenol-A liquid epoxy resin of hardening resin, ProductName JER828, epoxide equivalent 185g/
Eq), the 1- benzyl -2- phenylimidazole as hardening accelerator (chemical conversion industry company of four countries manufactures, ProductName 1B2PZ) and bag
The embodiment 1 of the varnish form of the polyamide-imide resin containing the structure shown in the structure shown in formula (1) and formula (2) to
Any one of 5 polyamide-imide resin.The combination that any one of thermosetting resin composition 1 to 5 is all discussed further below
Thing：The carboxyl equivalent of the polyamide being calculated according to the acid number of polyamide-imide resin and the epoxy radicals of epoxy resin
The equivalent proportion of equivalent is 1/1, and the hardening containing 1 mass parts with respect to the polyamide-imide resin of every 100 mass parts promotees
Enter agent.
(comparative example 4 to 6)
Comparison thermosetting resin composition (comparative example 4 to 6), the described thermosetting resin composition that compares contains
Have：(Mitsubishi Chemical Ind manufactures bisphenol-A liquid epoxy resin as thermosetting resin, ProductName JER828, and epoxy is worked as
Amount 185g/eq), as hardening accelerator 1- benzyl -2- phenylimidazole (chemical conversion industry company of four countries manufacture, ProductName
1B2PZ) and not comprise the structure shown in formula (1) and the polyamidoimide of any structure in the structure shown in formula (2)
Any one of the polyamide-imide resin of the comparative example 1 to 3 of varnish form of resin.Relatively thermosetting resin composition 1
To 3 any one composition being all discussed further below：The polyamide resin being calculated according to the acid number of polyamide-imide resin
The carboxyl equivalent of fat is 1/1 with the equivalent proportion of the epoxide equivalent of epoxy resin, and the polyamide with respect to every 100 mass parts
Imide resin contains the hardening accelerator of 1 mass parts.
[test example 1] assesses the alkali solubility of polyamide-imide resin
Will be hot for the comparison of the thermosetting resin composition of the embodiment 5 to 8 making in this way and comparative example 4 to 6
Curable resin composition, is applied on Copper Foil respectively in the way of dry film thickness is 25 μm, is dried 30 points with 90 DEG C of temperature
Clock and obtain desciccator diaphragm.Alps Engineering Co., Ltd. manufacture alkali development machine DV-40L in, with 30 DEG C of temperature,
Atomisation pressure 0.2MPa dissolves obtained desciccator diaphragm, the state of the film that sees drying, and root using 1 mass % aqueous sodium carbonate
The alkali solubility under thermosetting resin composition state is estimated according to following standards.
A：Can dissolve within 60 seconds.
B：Can dissolve within 120 seconds.
C：Can dissolve within 180 seconds.
D：Fail dissolving within 180 seconds.
[test example 2] measures tensile modulus of elasticity, tensile strength, percentage elongation
Thermosetting resin group by embodiment 5 to 8 made for the allotment recorded according to table 1 composition and comparative example 4 to 6
Compound is respectively coated on PET (PET), is dried 30 minutes with 90 DEG C of temperature in an oven, and with
180 DEG C harden 60 minutes, then strip down from PET thus making the cured film of 80 μm of thickness, cured film is cut established practice
Sizing, as test sample.
Determining instrument：Company of Shimadzu Seisakusho Ltd. manufactures, ProductName Autograph AG-Xplus.
Draw speed：5mm/min.
Sample size：10mm×150mm.
[test example 3] measures glass transition temperature, 5% weight reduces temperature
The cured film that the method recorded according to test example 2 is made cuts out a part, puts in following mensure containers
It is measured.
Determining instrument：Hitachi high-tech Sciences company manufactures, ProductName TG/DTA7220.
Atmosphere：In the air.
Temperature of the measurement：25 DEG C to 400 DEG C.
[test example 4] assessment dielectric property (dielectric constant, dielectric loss angle tangent)
The cured film that the method recorded according to test example 2 is made cuts out a part, is entered using following determining instruments
Row measures.
Determining instrument：Keysight Technologies company manufactures, ProductName Network Analyzer E5071C.
Northeast the development of electronics applied company manufactures, cavity perturbation method Dielectric Coefficient device.
Frequency：1GHz.
Sample size：Wide 2mm × long 100mm × thickness 0.080mm.
Table 1
The alkali of the thermosetting composition of the embodiment 6 to 10 of the polyamideimide resin solution containing embodiment 1 to 5
Dissolubility, dielectric property are all very excellent.
On the other hand, the thermosetting group of the comparative example 4 to 6 of the polyamideimide resin solution containing comparative example 1 to 3
Comparatively speaking, some dielectric properties are poor, and alkali solubility is also poor for the thermosetting composition of compound and embodiment 6 to 10.
Industrial utilizability
Polyamide-imide resin provided by the present invention, is the excellent polyamidoimide tree containing carboxyl of alkali solubility
Fat.
Thermosetting resin composition provided by the present invention is to form alkali solubility, mechanical property and excellent heat resistance
Hardening thing composition, lift a concrete example for, be the thermosetting resin composition comprising epoxy resin.
The hardening thing of the thermosetting resin composition of the polyamide-imide resin containing the present invention is in mechanical property, resistance to
Hot, dielectric property aspect is excellent.Therefore, the polyamide-imide resin of the present invention can serve as the exhausted of flexible printing wiring board
Edge material, bonding agent, film raw material resin etc..In addition, the alkali solubility of the polyamide-imide resin of the present invention is excellent, thus logical
Cross and the polyamide-imide resin of the present invention is mixed with photoreactive material, photosensitive film or bonding agent can be made to make
With, and be now also used as the lining material of circuit substrate etc..
Claims (15)
1. a kind of polyamide-imide resin is it is characterised in that have the structure shown in following formulas (1) and following formula (2)
Shown structure：
X1It is the residue of the aliphatic diamine (a) of dimeric dibasic acid being 24 to 48 from carbon number, X2It is the aromatic diamine with carboxyl
B the residue of (), Y is separately cyclohexane ring or aromatic rings.
2. polyamide-imide resin according to claim 1 is it is characterised in that acid number is more than 30mgKOH/g.
3. polyamide-imide resin according to claim 1 and 2 it is characterised in that described from carbon number be 24 to 48
The containing ratio of the aliphatic diamine (a) of dimeric dibasic acid be 20 weight % to 60 weight %.
4. the polyamide-imide resin according to any claim in claims 1 to 3 is it is characterised in that described lead to
In the cyclohexane ring being represented with Y in formula (1) and described formula (2) and/or aromatic rings, the content of cyclohexane ring is with respect to aromatic rings
The mol ratio of content be 85/15 to 100/0.
5. the polyamide-imide resin according to any claim in Claims 1-4 is it is characterised in that described tool
The aromatic diamine (b) having carboxyl comprises selected from 3,5- diaminobenzoic acid and 5,5'- di-2-ethylhexylphosphine oxide (ortho-aminobenzoic acid)
In the group being formed more than a kind.
6. a kind of thermosetting resin composition is it is characterised in that contain any claim institute in good grounds claim 1 to 5
The polyamide-imide resin stated and thermal sclerosing material.
7. thermosetting resin composition according to claim 6 is it is characterised in that described thermal sclerosing material is epoxy
Resin.
8. the thermosetting resin composition according to claim 6 or 7 is it is characterised in that also contain thermmohardening accelerator.
9. a kind of hardening thing is it is characterised in that be the thermosetting tree according to any claim in claim 6 to 8
The hardening thing of oil/fat composition.
10. a kind of manufacture method of polyamide-imide resin is it is characterised in that possess：
Imidation step, make from carbon number be 24 to 48 dimeric dibasic acid aliphatic diamine (a), there is the aromatic series two of carboxyl
In amine (b) and the group that formed selected from hexamethylene -1,2,4- tricarboxylic acids -1,2- acid anhydride (c) and trimellitic anhydride (d) 1
Kind or 2 kinds reacted and obtained acid imide compound (A)；And
Amide imide step, makes the described acid imide compound (A) being obtained by described imidation step, with diisocyanate
Compound (e) is reacted, and obtains the polyamide-imide resin shown in following formulas (3),
In described formula (3), X is separately diamines residue, and Y is separately cyclohexane ring or aromatic rings, and Z is two different
The residue of cyanate esters (e), n is natural number.
11. the manufacture method of polyamide-imide resin according to claim 10 is it is characterised in that by described acid amides acyl
The acid number of the described polyamide-imide resin that imidization step obtains is more than 30mgKOH/g.
The manufacture method of 12. polyamide-imide resins according to claim 10 or 11 is it is characterised in that described be derived from
Carbon number is the addition of the aliphatic diamine (a) of 24 to 48 dimeric dibasic acid, be make described from carbon number be 24 to 48 dimeric dibasic acid
The containing ratio of aliphatic diamine (a) be the amount to 60 weight % for 20 weight %.
The manufacture method of 13. polyamide-imide resins according to any claim in claim 10 to 12, it is special
Levy and be, hexamethylene -1,2,4- tricarboxylic acids -1, the usage amount of 2- acid anhydride (c) with respect to the usage amount of trimellitic anhydride (d) mole
Ratio is 85/15 to 100/0.
The manufacture method of 14. polyamide-imide resins according to any claim in claim 10 to 13, it is special
Levy and be, the described aromatic diamine (b) with carboxyl comprises adjacent selected from 3,5- diaminobenzoic acid and 5,5'- di-2-ethylhexylphosphine oxide
In the group that aminobenzoic acid is formed more than a kind.
The manufacture method of 15. polyamide-imide resins according to any claim in claim 10 to 14, it is special
Levy and be, described diisocyanate cpd (e) is aliphatic isocyanates compound.
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| JP2015159407A JP5934419B1 (en) | 2015-08-12 | 2015-08-12 | Polyamideimide resin, thermosetting resin composition, cured product of the thermosetting resin composition, and method for producing polyamideimide resin |
| JP2015-159407 | 2015-08-12 |
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| CN108693702A (en) * | 2017-03-31 | 2018-10-23 | 太阳油墨制造株式会社 | Hardening resin composition, laminate structure, its solidfied material and electronic unit |
| CN110546219A (en) * | 2017-04-28 | 2019-12-06 | 马勒国际有限公司 | Bearing material, bearing and method |
| CN111333841A (en) * | 2020-03-20 | 2020-06-26 | 住井工业（湖南）有限公司 | Polyamide-imide resin, insulating film, insulated wire, coil, and motor |
| CN111574923A (en) * | 2020-05-28 | 2020-08-25 | 苏州东特绝缘科技有限公司 | Polyamide-imide insulating paint and preparation method thereof |
| CN113166410A (en) * | 2018-11-30 | 2021-07-23 | 太阳油墨制造株式会社 | Photosensitive thermosetting resin composition, dry film and printed wiring board |
| CN114058324A (en) * | 2020-12-15 | 2022-02-18 | 东洋油墨Sc控股株式会社 | Thermosetting resin composition and use thereof |
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| JPWO2016171101A1 (en) * | 2015-04-20 | 2018-02-15 | 宇部興産株式会社 | Polyimide, curable resin composition, cured product |
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| US11964730B2 (en) | 2021-05-22 | 2024-04-23 | Sram, Llc | Controller indication |
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| CN108693702A (en) * | 2017-03-31 | 2018-10-23 | 太阳油墨制造株式会社 | Hardening resin composition, laminate structure, its solidfied material and electronic unit |
| CN110546219A (en) * | 2017-04-28 | 2019-12-06 | 马勒国际有限公司 | Bearing material, bearing and method |
| CN113166410A (en) * | 2018-11-30 | 2021-07-23 | 太阳油墨制造株式会社 | Photosensitive thermosetting resin composition, dry film and printed wiring board |
| CN111333841A (en) * | 2020-03-20 | 2020-06-26 | 住井工业（湖南）有限公司 | Polyamide-imide resin, insulating film, insulated wire, coil, and motor |
| CN111574923A (en) * | 2020-05-28 | 2020-08-25 | 苏州东特绝缘科技有限公司 | Polyamide-imide insulating paint and preparation method thereof |
| CN114058324A (en) * | 2020-12-15 | 2022-02-18 | 东洋油墨Sc控股株式会社 | Thermosetting resin composition and use thereof |
| CN114058324B (en) * | 2020-12-15 | 2022-06-17 | 东洋油墨Sc控股株式会社 | Thermosetting resin composition and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5934419B1 (en) | 2016-06-15 |
| JP2017036407A (en) | 2017-02-16 |
| CN106432725B (en) | 2018-03-27 |
| TWI574998B (en) | 2017-03-21 |
| TW201706335A (en) | 2017-02-16 |
| KR101713996B1 (en) | 2017-03-07 |
| KR20170020220A (en) | 2017-02-22 |
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