CN106554618A

CN106554618A - Thermosetting compositionss and application thereof

Info

Publication number: CN106554618A
Application number: CN201610820103.1A
Authority: CN
Inventors: 中原铁舟; 小针优纪; 近藤学; 江头友弘; 横手友纪
Original assignee: JNC Corp
Current assignee: JNC Corp
Priority date: 2015-09-24
Filing date: 2016-09-13
Publication date: 2017-04-05
Also published as: JP6693361B2; TW201725224A; JP2017061680A; KR20170036622A; TWI709590B

Abstract

The present invention relates to a kind of thermosetting compositionss and application thereof, the thermosetting compositionss are the compositionss comprising polyesteramide acid, the epoxide with siloxanes key knot position, the epoxide and epoxy curing agent without siloxanes key knot position, and polyesteramide acid is by being obtained with tetracarboxylic dianhydride, diamidogen and multi-hydroxy compound as required material composition is reacted.By the thermosetting compositionss of the present invention, can obtain that light resistance, flatness are especially excellent, the also excellent cured film in chemical-resistant, resistance to water, the adhesion to basal substrates such as glass, the transparency, scratch resistance, the coatings such as thermostability, solvent resistance/acid resistance/alkali resistance.

Description

Thermosetting compositionss and application thereof

Technical field

The present invention relates to a kind of can be used to form the insulant in electronic component, the passivating film in semiconductor device, delay The interlayer dielectric rushed in film, interlayer dielectric or planarization film, or liquid crystal display cells or colored filter protecting film Deng thermosetting compositionss, the hyaline membrane using the thermosetting compositionss and the electronic component comprising the film.

Background technology

In the manufacturing process of the elements such as liquid crystal display cells, the various chemistry such as organic solvent, acid, aqueous slkali are carried out sometimes Product process, or when by sputtering (sputtering) and film forming wired electric pole, surface is locally heated by as high temperature.Cause This, it is deterioration, damage sometimes for the surface for preventing various elements, rotten and surface protection film is set.For these protecting film, Require to can tolerate each characteristic of the various process in manufacturing process as above.Specifically, it is desirable to thermostability, solvent resistant The chemical-resistants such as property/acid resistance/alkali resistance, resistance to water, the adhesion to basal substrates such as glass, the transparency, scratch resistance, Coating, flatness, light resistance etc..And, in the high visual angle of propulsion liquid crystal display cells, high-speed response, High precision Under the present situation of contour performance-based, in the case of as protective films of color filters, the material that planarization characteristics are improved is expected Material.

With regard to light resistance, so far it is important that carrying out ultraviolet to carry out the surface clean of protecting film The process of (ultraviolet, UV) ozone.However, particularly in recent years, in lateral electric field mode protective films of color filters In, in order to improve the coating of photonasty spacer (photo spacer), become desirable at the ultraviolet and ozone of higher energy Reason, and, increase polymer stabilizing orientation (Polymer Sustained Alignment, PSA) pattern etc. photopolymerization operation or The ultraviolet exposure operation such as light orientation operation of alignment films, light resistance become very important characteristic.

As the Protective coatings with these excellent specific properties, the polyamic acid composition containing silicon is there are (with reference to specially Sharp document 1), polyesteramide acid composition (with reference to patent documentation 2, patent documentation 3).Combine with regard to the polyamic acid containing silicon , although flatness is good, there is thermostability insufficient, the shortcoming of alkali resistance difference in thing.The polyesteramide acid group of patent documentation 2 There is flatness and the not sufficient shortcoming of thermostability in compound.The polyesteramide acid composition of patent documentation 3 is flatness, heat-resisting The very excellent material of property and chemical-resistant, but have the disadvantage that：Light resistance is simultaneously insufficient, ultraviolet and ozone process or In ultraviolet exposure operation, the transparency is reduced.For accordingly, as Protective coatings, the insufficient satisfaction of described any one material Light resistance, flatness, thermostability, chemical-resistant and other each characteristics.

[prior art literature]

[patent documentation]

[patent documentation 1] Japanese Patent Laid-Open 9-291150 publication

[patent documentation 2] Japanese Patent Laid-Open 2005-105264 publication

[patent documentation 3] Japanese Patent Laid-Open 2008-156546 publication

The content of the invention

[invention problem to be solved]

The problem of the present invention is to provide chemical-resistants such as a kind of thermostability, solvent resistance/acid resistance/alkali resistance, resistance to Aqueouss, the adhesion to basal substrates such as glass, the transparency, scratch resistance, coating are excellent, particularly flatness, light resistance Excellent cured film and the electronic component comprising the compositionss for providing the cured film.

[technological means of solve problem]

The present inventor et al. has carried out making great efforts research to solve the problem, as a result finds by following combination Thing and make said composition hardening and the cured film of gained may achieve the purpose, so as to complete the present invention, the compositionss bag Containing polyesteramide acid, the epoxide with siloxanes key knot position, with siloxanes key knot position epoxide, And epoxy curing agent, the polyesteramide acid is by the compound comprising tetracarboxylic dianhydride, diamidogen and multi-hydroxy compound React and obtain.

The present invention includes following composition.

[1] a kind of thermosetting compositionss, which is comprising polyesteramide acid, the epoxy compound with siloxanes key knot position The compositionss of thing, the not epoxide with siloxanes key knot position and epoxy curing agent, wherein, polyesteramide acid is logical Cross with tetracarboxylic dianhydride, diamidogen and multi-hydroxy compound and obtained as required material composition is reacted, and be by making X mole of tetracarboxylic dianhydride, the multi-hydroxy compound of Y mole of diamidogen and Z mole are with following formula (1) and the relation of formula (2) The polyesteramide acid that the ratio of establishment is reacted and obtained,

0.2≤Z/Y≤8.0…(1)

0.2≤(Y+Z)/X≤5.0…(2)

Polyesteramide acid has construction unit and the construction unit represented by formula (4) represented by following formulas (3)；

Relative to polyesteramide 100 weight portions of acid, the epoxide with siloxanes key knot position and with silica The epoxide at alkane bond position adds up to 20 weight portion～400 weight portions；

Relative to total 100 weight portions of the epoxide, epoxy curing agent is 0 weight portion～60 weight portion；And And,

The ratio of the epoxide with siloxanes key knot position in the total amount of the epoxide is 0.5 weight Amount %～70 weight %,

(R¹It is tetracarboxylic dianhydride's residue, R²It is diamidogen residue, R³It is multi-hydroxy compounds residues).

[2] the thermosetting compositionss according to [1], the wherein material composition of polyesteramide acid further include unitary Alcohol.

[3] the thermosetting compositionss according to [2], wherein monohydric alcohol is selected from isopropanol, 1-propenol-3, benzylalcohol, first One or more of base Hydroxyethyl Acrylate, dihydroxypropane single-ether and 3- ethyl -3- hydroxymethyl oxetanes.

[4] the thermosetting compositionss according to any one of [1] to [3], the wherein material composition of polyesteramide acid Styrene-maleic anhydride copolymer is included further.

[5] the thermosetting compositionss according to any one of [1] to [4], the wherein weight average of polyesteramide acid Molecular weight is 1,000～200,000.

[6] according to the thermosetting compositionss any one of [1] to [5], wherein tetracarboxylic dianhydride be selected from 3,3 ', 4,4 '-sulfobenzide. tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 2,2- [double (3,4- dicarboxyphenyis)] One or more of hexafluoropropane dianhydride, 1,2,3,4- butane tetracarboxylic acid dianhydrides and ethylene glycol double (dehydration trimellitates).

[7] the thermosetting compositionss according to any one of [1] to [6], wherein diamidogen is selected from 3,3 '-diaminourea One or more of sulfobenzide. and double [4- (3- amino-benzene oxygens) phenyl] sulfones.

[8] the thermosetting compositionss according to any one of [1] to [7], wherein multi-hydroxy compound is to be selected from Ethylene glycol, Propylene Glycol, BDO, 1,5-PD, 1,6- hexanediol, 1,7- heptandiols, 1,8- ethohexadiols and different trimerization One or more of cyanic acid three (2- hydroxyethyls) ester.

[9] the thermosetting compositionss according to any one of [1] to [8], wherein with siloxanes key knot position Epoxide be in group selected from the compound represented by the compound represented by following formula (5) and formula (6) at least One kind,

(R⁴、R⁵And R⁶It is separately hydrogen, hydroxyl, the organic group of carbon number 1～26 or the organic group with epoxy radicals, R⁷It is separately hydrogen, the organic group of carbon number 1～26 or the organic group with epoxy radicals, R⁴、R⁵、R⁶And R⁷At least one It is the organic group with epoxy radicals, m is more than 2 integer, R⁴Or R⁵Also can be from the R being bonded on different Si⁴Or R⁵Bond and Form siloxanes ring, also, R⁶And R⁷Can also be bonded and form siloxanes ring)

(R⁸、R⁹、R¹⁰、R¹¹It is separately hydrogen or the organic group of carbon number 1～26, R¹²And R¹³Be separately hydrogen, The organic group of carbon number 1～26 or the organic group with epoxy radicals, R¹²And R¹³At least one be the organic group with epoxy radicals, n For more than 1 integer, R⁸Or R⁹Also can be from the R being bonded on different Si⁸、R⁹、R¹⁰, or R¹¹It is bonded and forms siloxanes ring, and And, R¹⁰Or R¹¹Also can be from the R being bonded on different Si⁸、R⁹、R¹⁰, or R¹¹It is bonded and forms siloxanes ring).

[10] the thermosetting compositionss according to any one of [1] to [9], wherein with siloxanes key knot position Epoxide is selected from by double with double [2- (3, the 4- expoxycyclohexyl) ethyl] tetramethyl disiloxanes of 1,3-, 1,3- (3- glycidoxypropyls) tetramethyl disiloxane, 3- glycidoxypropyltrimewasxysilanes are entered for material composition The copolymer that row reacts and obtains, and by with 3- glycidoxypropyltrimewasxysilanes, phenyl trimethoxy silicon At least one in the group that the copolymer that alkane and trimethylmethoxysilane are reacted and obtained by material composition is constituted.

[11] the thermosetting compositionss according to any one of [1] to [9], wherein epoxy curing agent is selected from inclined benzene One or more of three anhydride, hexahydro trimellitic anhydride and 2- undecyl imidazoles.

[12] the thermosetting compositionss according to [1], wherein tetracarboxylic dianhydride is 3,3 ', 4,4 '-diphenyl ether four Carboxylic acid dianhydride or 1,2,3,4- butane tetracarboxylic acid dianhydrides；

Diamidogen is 3,3 '-diamino diphenyl sulfone；

Multi-hydroxy compound is BDO；

Epoxide with siloxanes key knot position is by with 3- glycidoxypropyltrimewasxysilanes Obtained for material composition is reacted, weight average molecular weight is 1,000～200,000 copolymer；

The epoxide with siloxanes key knot position is not 2- [4- (2,3- epoxy radicals propoxyl group) phenyl] -2- [4- 1,1- double [4- ([2,3- epoxy radicals propoxyl group] phenyl) ethyl] phenyl] propane；

Epoxy curing agent is trimellitic anhydride or 2- undecyl imidazoles；Also,

Further contain 3- methoxy methyl propionates or propylene glycol methyl ether acetate as solvent.

[13] a kind of cured film, which is by being obtained according to the thermosetting compositionss any one of [1] to [12].

[14] a kind of colored filter, which uses the cured film described in basis [13] as protecting film.

[15] a kind of liquid crystal display cells, which is using the colored filter according to [14].

[16] a kind of solid-state imager, which is using the colored filter according to [14].

[17] a kind of liquid crystal display cells, which is used according to the cured film described in [13] as being formed in thin film transistor (TFT) The transparent insulating film of (Thin Film Transistor, TFT) and transparency electrode between.

[18] a kind of liquid crystal display cells, which is used according to the cured film described in [13] as being formed in transparency electrode and take To the transparent insulating film between film.

[19] a kind of touch panel device, which uses saturating as formed on the transparent electrodes according to the cured film described in [13] Bright dielectric film.

[20] a kind of light emitting diode (Light Emitting Diode, LED) luminous body, which is using according to [13] Cured film as protecting film.

[The effect of invention]

The thermosetting compositionss of the preferred embodiment of the present invention are the especially excellent materials of flatness and light resistance, As color liquid crystal display device protective films of color filters and in the case of use, carry can display quality and reliability It is high.And, heated by the thermosetting compositionss to the preferred embodiment of the present invention and the cured film of gained is saturating The aspect of bright property, chemical-resistant, adhesion and resistant sputtering also obtains balance, and practicality is very high.Particularly act effectively as The protecting film of the colored filter manufactured using staining, pigment dispersion method, electrodeposition process and print process.And, can also make Use for the protecting film and transparent insulating film of various optical materials.

Specific embodiment

1. thermosetting compositionss

The thermosetting compositionss of the present invention are comprising polyesteramide acid, the epoxy compound with siloxanes key knot position The compositionss of thing, the not epoxide with siloxanes key knot position and epoxy curing agent, the polyesteramide acid is to pass through Obtained with tetracarboxylic dianhydride, diamidogen and multi-hydroxy compound as required material composition is reacted.The thermosetting Compositionss are characterised by：In said composition, relative to polyesteramide 100 weight portions of acid, the ring with siloxanes key knot position Oxygen compound adds up to 20 weight portion～400 weight portions with the not epoxide with siloxanes key knot position, relative to Total 100 weight portions of the epoxide, epoxy curing agent is 0 weight portion～60 weight portion, also, the epoxy compound The ratio of the epoxide with siloxanes key knot position in the total amount of thing is 0.5 weight %～70 weight %.This Bright thermosetting compositionss can also be in the range of the effect for obtaining the present invention further containing the other compositions beyond described.

The acid of 1-1. polyesteramides

Polyesteramide acid is by being carried out with tetracarboxylic dianhydride, diamidogen and multi-hydroxy compound as required material composition React and obtain.More specifically, by making the multi-hydroxy of X mole of tetracarboxylic dianhydride, Y mole of diamidogen and Z mole Compound is reacted with the ratio that the relation of following formula (1) and formula (2) is set up and is obtained.

0.2≤Z/Y≤8.0…(1)

0.2≤(Y+Z)/X≤5.0…(2)

Polyesteramide acid has construction unit and the construction unit represented by formula (4) represented by following formula (3).

In formula (3) and formula (4), R¹It is the residue that two-CO-O-CO- are removed from tetracarboxylic dianhydride, preferably carbon Number is 2～30 organic group.R²It is to remove two-NH from diamidogen₂Residue, preferably carbon number is 2～30 organic group. R³It is the residue that two-OH are removed from multi-hydroxy compound, preferably carbon number is 2～20 organic group.

The synthesis of polyesteramide acid at least needs solvent, and the solvent can be made directly to remain and make in view of operability etc. Liquid or gelatinous thermosetting compositionss, or also the solvent can be removed and make the solid, shaped in view of carrying property etc. Compositionss.And, the synthesis of polyesteramide acid also can optionally comprising selected from monohydroxy compound and phenylethylene-maleic anhydride The compound of one or more of copolymer as raw material, wherein, preferably comprise monohydroxy compound.And, polyesteramide acid Synthesis also can be not undermining in the range of the purpose of the present invention, optionally comprising other compounds beyond described as original Material.

1-1-1. tetracarboxylic dianhydride

In the present invention, the materials'use tetracarboxylic dianhydride sour to obtain polyesteramide.Preferred tetracarboxylic dianhydride's Concrete example can enumerate 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide. tetracarboxylic dianhydride, 2,2 ', 3,3 '-sulfobenzide. tetrabasic carboxylic acid two Acid anhydride, 2,3,3 ', 4 '-sulfobenzide. tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 2,2 ', 3,3 '-diphenyl Ether tetracarboxylic dianhydride, 2,3,3 ', 4 '-diphenyl ether tetracarboxylic dianhydride, 2,2- [double (3,4- dicarboxyphenyis)] HFC-236fa two Double (dehydration the trimellitate) (trade names of acid anhydride, 1,2,3,4- butane tetracarboxylic acid dianhydrides, ethylene glycol；TMEG-100, new Japan Chemical Limited company), Tetramethylene. tetracarboxylic dianhydride, methyl cyclobutane tetracarboxylic dianhydride, Pentamethylene. tetracarboxylic dianhydride, hexamethylene four Carboxylic acid dianhydride, ethane tetracarboxylic dianhydride and butane tetracarboxylic acid dianhydride.Can be using one or more of these tetracarboxylic dianhydrides.

In these tetracarboxylic dianhydrides, more preferably give good transparency 3,3 ', 4,4 '-sulfobenzide. tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 2,2- [double (3,4- dicarboxyphenyis)] hexafluoropropane dianhydride, 1,2,3,4- fourths Alkane tetracarboxylic dianhydride and TMEG-100, particularly preferred 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl Sulfone tetracarboxylic dianhydride and 1,2,3,4- butane tetracarboxylic acid dianhydrides.

1-1-2. diamidogen

In the present invention, the materials'use diamidogen sour to obtain polyesteramide.The concrete example of preferred diamidogen can be enumerated 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, double [4- (4- aminobenzene oxygen Base) phenyl] sulfone, double [4- (3- amino-benzene oxygens) phenyl] sulfones, double [3- (4- amino-benzene oxygens) phenyl] sulfones, [4- (4- aminobenzenes Epoxide) phenyl] [3- (4- amino-benzene oxygens) phenyl] sulfone, [4- (3- amino-benzene oxygens) phenyl] [3- (4- amino-benzene oxygens) benzene Base] double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa of sulfone and 2,2-.Can be using one or more of these diamidogen.

In these diamidogen, the 3 of good transparency is more preferably given, 3 '-diamino diphenyl sulfone and double [4- (3- aminobenzenes Epoxide) phenyl] sulfone, particularly preferred 3,3 '-diamino diphenyl sulfone.

1-1-3. multi-hydroxy compounds

In the present invention, the materials'use multi-hydroxy compound sour to obtain polyesteramide.Preferred multi-hydroxy The concrete example of compound can enumerate ethylene glycol, diethylene glycol, triethylene glycol, TEG, weight average molecular weight for 1,000 with Under Polyethylene Glycol, Propylene Glycol, dipropylene glycol, tripropylene glycol, four Propylene Glycol, weight average molecular weight be less than 1,000 it is poly- Propylene Glycol, 1,2- butanediols, 1,3 butylene glycol, BDO, 1,2- pentanediols, 1,5-PD, 2,4- pentanediols, 1,2, Penta triols of 5-, 1,2- hexanediol, 1,6- hexanediol, 2,5- hexanediol, 1,2,6- hexanetriols, 1,2- heptandiols, 1,7- heptandiols, 1,2,7- heptan triol, 1,2- ethohexadiols, 1,8- ethohexadiols, 3,6- ethohexadiols, 1,2,8- pungent triols, 1,2- nonanediols, 1,9- nonyls Glycol, 1,2,9- nonyl triols, 1,2- decanediols, decamethylene-glycol, 1,2,10- last of the ten Heavenly stems triols, 1,2- dodecanediols, 1,12- ten It is dioxane glycol, glycerol, trimethylolpropane, tetramethylolmethane, dipentaerythritol, fulminuric acid three (2- hydroxyethyls) ester, double Phenol A (2,2- double (4- hydroxy phenyls) propane), bisphenol S (double (4- hydroxy phenyls) sulfones), Bisphenol F (double (4- hydroxy phenyls) first Alkane), diethanolamine and triethanolamine.Can be using one or more of these multi-hydroxy compounds.

In these multi-hydroxy compounds, the ethylene glycol of favorable solubility more preferably in a solvent, Propylene Glycol, Isosorbide-5-Nitrae-fourth Glycol, 1,5-PD, 1,6- hexanediol, 1,7- heptandiols, 1,8- ethohexadiols and fulminuric acid three (2- hydroxyethyls) Ester, particularly preferred BDO, 1,5-PD and 1,6- hexanediol.

1-1-4. monohydroxy compound

In the present invention, the material to obtain polyesteramide acid can use monohydroxy compound.By using monohydroxy Compound, improves can the storage stability of thermosetting compositionss.The concrete example of preferred monohydroxy compound can enumerate first Alcohol, ethanol, 1- propanol, isopropanol, 1-propenol-3, benzylalcohol, hydroxyethyl methacrylate, dihydroxypropane single-ether, Propylene Glycol list first Ether, DPE, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol monoethyl ether, diethylene glycol monoethyl ether, two Glycol monoethyl ether, phenol, Borneolum Syntheticum (borneol), maltol (maltol), linalool (linalol), terpineol (terpineol), dimethyl benzyl carbinol (dimethyl benzylcarbinol), and 3- ethyl -3- hydroxymethyl oxa- rings Butane.Can be using one or more of these monohydroxy compounds.

More preferably isopropanol, 1-propenol-3, benzylalcohol, hydroxyethyl methacrylate, Propylene Glycol in these monohydroxy compounds Single ether or 3- ethyl -3- hydroxymethyl oxetanes.If the polyester that consideration will be formed using these monohydroxy compounds Amic acid and the epoxide with siloxanes key knot position, the epoxide and ring without siloxanes key knot position Oxygen sclerosing agent mix in the case of intermiscibility, or coating of the thermosetting compositionss on colored filter, then monohydroxy Compound particularly preferably uses benzylalcohol.

Relative to 100 weight portion of total amount of tetracarboxylic dianhydride, diamidogen and multi-hydroxy compound, 0 weight is preferably comprised The monohydroxy compound of part～300 weight portions and reacted.More preferably 5 weight portion～200 weight portions.

1-1-5. styrene-maleic anhydride copolymer

And, the polyesteramide acid used in the present invention can also be added in the raw material with more than three anhydride groups Compound and synthesize.The raising of the transparency of the polyesteramide acid added the compound with more than three anhydride groups and synthesize Expected, therefore preferably.The example of the compound with more than three anhydride groups can enumerate styrene-maleic anhydride copolymer Thing.Ratio with regard to constituting each composition of styrene-maleic anhydride copolymer, the mol ratio of phenylethylene/maleic anhydride is 0.5～ 4, preferably 1～3.Furthermore, more preferably 1 or 2, particularly preferred 1.

The concrete example of styrene-maleic anhydride copolymer can be enumerated SMA3000P, SMA2000P, SMA1000P and (be business The name of an article；River crude oil limited company).The good SMA1000P of particularly preferred thermostability and alkali resistance in these commercially available products.

Contain 0 weight preferably with respect to 100 weight portion of total amount of tetracarboxylic dianhydride, diamidogen and multi-hydroxy compound The styrene-maleic anhydride copolymer of amount part～500 weight portion.More preferably 10 weight portion～300 weight portions.

1-1-6. has the amino silane compounds of an amino

In the synthesis of polyesteramide acid, can also not undermine in the range of the purpose of the present invention, optionally comprising described Used as raw material, the example of this kind of other raw materials can enumerate the amino silane chemical combination with an amino to other raw materials in addition Thing.Amino silane compounds with an amino are led in end to the anhydride group reaction with the end of polyesteramide acid Enter silylation.If using the thermosetting compositionss of the present invention containing the acid of following polyesteramide, the painting of gained can be improved The acid resistance of film, the polyesteramide acid are to be reacted by amino silane compounds of the addition with an amino and obtained .In addition, in the case where being reacted with the composition of the monomer, can also add monohydroxy compound and there is an amino Amino silane compounds this both and reacted.

The concrete example of the amino silane compounds preferably with an amino used in the present invention can be enumerated：3- ammonia Base propyl trimethoxy silicane, APTES, 3- amino propyl methyl dimethoxysilanes, 3- aminopropans Ylmethyl diethoxy silane, 4- aminobutyl trimethoxy silanes, 4- ammobutyltriethoxysilanes, 4- aminobutyl first Base diethoxy silane, p-aminophenyl trimethoxy silane, p-aminophenyl triethoxysilane, p-aminophenyl ylmethyl two Methoxy silane, p-aminophenyl methyldiethoxysilane, m-aminophenyl base trimethoxy silane and m-aminophenyl ylmethyl Diethoxy silane.Can use these that there are one or more of amino silane compounds of an amino.

During these have amino silane compounds of an amino, the good 3- aminopropyls of the acid resistance of more preferably film Triethoxysilane and p-aminophenyl trimethoxy silane, from from the viewpoint of acid resistance, intermiscibility, particularly preferred 3- amino Propyl-triethoxysilicane.

Preferably with respect to 100 weight portion of total amount of tetracarboxylic dianhydride, diamidogen and multi-hydroxy compound, containing 0 weight The amino silane compounds with an amino of part～300 weight portions.More preferably 5 weight portion～200 weight portions.

Solvent used in the synthetic reaction of 1-1-7. polyesteramides acid

The concrete example of the solvent used in the synthetic reaction sour to obtain polyesteramide can enumerate diethylene glycol diformazan Ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetic acid esters, ethylene glycol monoethylether acetate, Propylene glycol methyl ether acetate, 3- methoxy methyl propionates, 3- ethoxyl ethyl propionates, ethyl lactate, Ketohexamethylene, N- methyl- 2-Pyrrolidone and N,N-dimethylacetamide.Preferred propylene glycol methyl ether acetate, 3- methoxypropionic acid first in these solvents Ester or diethylene glycol methyl ethyl ether.

The synthetic method of 1-1-8. polyesteramides acid

Used in the present invention polyesteramide acid synthetic method be make in the solvent X mole of tetracarboxylic dianhydride, Y mole of diamidogen, and multi-hydroxy compound Z molar reactives.Now, X, Y and Z are preferably set at following between these X, Y and Z The ratio that the relation of formula (1) and formula (2) is set up.If the scope, then polyesteramide acid dissolubility in a solvent is high, therefore The coating of compositionss is improved, and as a result can obtain the excellent cured film of flatness.

0.2≤Z/Y≤8.0…(1)

0.2≤(Y+Z)/X≤5.0…(2)

In formula (1), preferably 0.7≤Z/Y≤7.0, more preferably 1.0≤Z/Y≤5.0.And, in formula (2), preferably 0.5≤(Y+Z)/X≤4.0, more preferably 0.6≤(Y+Z)/X≤2.0.

Polyesteramide acid used in the present invention is the superfluous bar using X relative to Y+Z under the cited reaction conditions Under part, the molecule than having amido or hydroxyl in end generate superfluously end have anhydride group (- CO-O-CO-) point Son.In the case where being reacted with the composition of this kind of monomer, end is carried out for the anhydride group reaction with molecular end Esterification, can optionally add described monohydroxy compound.Reacted and the polyester of gained by adding monohydroxy compound Amic acid can improve the intermiscibility with epoxide and epoxy curing agent, and can improve the present invention's comprising these compounds The coating of thermosetting compositionss.

If using 100 weight relative to total 100 weight portions of tetracarboxylic dianhydride, diamidogen and multi-hydroxy compound Reaction dissolvent more than part, then reacting successfully is carried out, therefore preferably.Reaction with 40 DEG C～200 DEG C react 0.2 hour～ It is advisable within 20 hours.

Order reaction raw materials made an addition in response system is not particularly limited.That is, following any side can be used Method：Tetracarboxylic dianhydride is added into reaction dissolvent simultaneously with diamidogen and multi-hydroxy compound；Make diamidogen and multi-hydroxy After compound is dissolved in reaction dissolvent, add tetracarboxylic dianhydride；Tetracarboxylic dianhydride is made to be reacted with multi-hydroxy compound in advance Afterwards, add diamidogen in its product；Or after tetracarboxylic dianhydride is reacted with diamidogen in advance, add in its product Multi-hydroxy compound etc..

In the case where reacting the amino silane compounds with an amino, in tetracarboxylic dianhydride and diamidogen and After the reaction of multi-hydroxy compound terminates, reactant liquor is cooled to after less than 40 DEG C, amino silicone of the addition with an amino Hydride compounds, react at 10 DEG C～40 DEG C and are advisable for 0.1 hour～6 hours.And, can be single in the addition of the random time point of reaction Hydroxy compounds.

The polyesteramide acid for synthesizing as mentioned above is represented comprising the construction unit and formula (4) represented by the formula (3) Construction unit, and its end is derived from the tetracarboxylic dianhydride as raw material, the anhydride group of diamidogen or multi-hydroxy compound, ammonia Additive beyond base or hydroxyl, or these compounds constitutes its end.By comprising this kind of composition, hardening becomes good.

The weight average molecular weight of the polyesteramide acid of gained is preferably 1,000～200,000, more preferably 3,000～ 50,000.If being in these scopes, flatness and thermostability become good.

Weight average molecular weight in this specification is using gel permeation chromatography (Gel Permeation Chromatography, GPC) method (tubing string temperature：35 DEG C, flow velocity：The value of polystyrene conversion 1ml/min) obtained.Mark Accurate polystyrene is using the polystyrene (such as Agilent Technologies (Agilent that molecular weight is 645～132900 Technologies) polystyrene calibration set group (calibration kit) PL2010-0102 of limited company), tubing string Using PLgel MIXED-D (Agilent Technologies Co., Ltd.), tetrahydrofuran (Tetrahydrofuran, THF) can be used It is measured as mobile phase.In addition, the weight average molecular weight of the commercially available product in this specification is catalogue (catalogue) Record value.

1-2. epoxide

Epoxide used in the present invention can use the epoxide with siloxanes key knot position and not have There is the epoxide of siloxanes key knot position.Make from the effect for not undermining the present invention described later with siloxanes key knot From the viewpoint of the characteristic of the epoxide of position manifests, the epoxide preferably with siloxanes key knot position is in the ring Ratio in the total amount of oxygen compound is 0.5 weight %～70 weight %.

1-2-1. has the epoxide of siloxanes key knot position

As long as the epoxide with siloxanes key knot position used in the present invention is hard with the heat for forming the present invention The intermiscibility of the other compositions of the property changed compositionss is good, then be not particularly limited.Epoxide with siloxanes key knot position At least one in the group of the compound represented by the compound being preferably selected from by represented by following formula (5) and formula (6).

In formula (5), R⁴、R⁵And R⁶Separately for hydrogen, hydroxyl, the organic group of carbon number 1～26 or have epoxy radicals Organic group, R⁷It is separately hydrogen, the organic group of carbon number 1～26 or the organic group with epoxy radicals, R⁴、R⁵、R⁶And R⁷'s At least one is the organic group with epoxy radicals.M is more than 2 integer, R⁴Or R⁵Also can be from the R being bonded on different Si⁴Or R⁵It is bonded and forms siloxanes ring, also, R⁶And R⁷Can also be bonded and form siloxanes ring.

R⁴、R⁵And R⁶Carbon number 1～26 organic group be straight-chain alkyl, branch-like alkyl, cyclic alkyl, comprising ring-type The alkyl of alkyl, aromatic rings, the base comprising aromatic rings etc., the arbitrary methylene (CH of these bases₂) also can be by comprising O, NH, N Base or base comprising Si replace, and, the arbitrary hydrogen of these bases also can be replaced by fluorine.

The concrete example of straight-chain alkyl and branch-like alkyl is methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, uncle Butyl, amyl group, tertiary pentyl, hexyl, 2,3- dimethylbutane -2- bases, octyl group, 6- methylheptyls, decyl, dodecyl, 14 Alkyl, pentadecyl, cetyl and octadecyl.

The concrete example of cyclic alkyl and the alkyl comprising cyclic alkyl is cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, 4- Methylcyclohexyl, bicyclic [2.2.1] heptane -2- bases, bicyclic [2.2.1] hept- 5- alkene -2- bases, 2- cyclohexyl-ethyls, 2- (hexamethylene - 3- alkene -1- bases) ethyl, 2- cycloheptylethyls, 2- (bicyclic [2.2.1] hept- 5- alkene -2- bases) ethyl, 3- Cyclohexylpropyls, 4- (tert-butyl group) cyclohexyl and adamantyl.

The concrete example of aromatic rings and the base comprising aromatic rings is phenyl, benzyl, phenethyl, 4- isopropyl phenyls, equal front three Phenyl, 3,5- diethyl phenyls, 4- isobutyl phenenyls, 2,6- diethyl phenyls, naphthalene -2- bases, 1,1 '-xenyl, 4 '-(tertiary fourth Base)-[1,1 '-xenyl] -4- bases, 2,4,6- triisopropyl phenyl, 4 '-heptyl-[1,1 '-xenyl] -4- bases, 12- ((2- Benzoylbenzoyl) epoxide) dodecyl and anthracene -9- bases.

Arbitrary methylene (CH₂) by comprising O, N or Si base replace the base concrete example be acetoxy-methyl, 3- methoxyl group -3- oxopropyls, 3- (2- methoxy ethoxy) propyl group, 2,5,8, the 11- tetra- oxa- tetradecane -14- bases, 2,5,8, Tetra- oxa- heptadecane -17- bases of 11-, 11,11- dimethoxy undecyls, 2- (dimethylamino) ethyl, 2- (diethyl aminos Base) ethyl, tetrahydrofuran -3- bases, tetrahydrochysene -2H- pyrans -4- bases, 3- ((tetrahydrofuran -3- bases) methoxyl group) propyl group, 10- (1, 3- dioxolane -2- bases) decyl, 10- (1,3- diox -2- bases) decyl, morpholinyl, 4- methoxyl group -3,5- dimethyl Benzyl, hydroxymethyl, 2- hydroxyethyls, 3- hydroxypropyls, 1- carboxy ethyls, 4- hydroxybutyls, 4- hydroxyl -3- oxo butyl, TMS, (TMS) methyl, 3- (TMS) propyl group, 2- (2,4,4,6,6,8,8- seven methyl- 1,3,5,7- tetra- oxa- -2,4,6,8- tetra- silicon cyclooctane -2- bases) ethyl, 2- (dimethyl (phenyl) silylation) ethyl, methoxy Base, ethyoxyl, propoxyl group, isopropoxy, propyl- 1- alkene -2- base epoxides, butoxy, tert-butoxy, sec-butoxy, isobutoxy, Tertiary pentyl epoxide, hexyl epoxide, 2- ethyl-butoxies, (3- methyl amyls) epoxide, (2- methyl hexane -2- bases) epoxide, octyl group Epoxide, (2- ethylhexyls) epoxide, decyl epoxide, 2- methoxy ethoxy, 2- ethoxy ethoxies, (1- methoxy propane -2- Base) epoxide, 2- (2- methoxy ethoxy) ethyoxyl, 2- Butoxyethoxies, (3- ethyl hexyl acyl groups) epoxide, dodecyl oxygen Base, tridecyl epoxide, cetyl epoxide, octadecyl epoxide, stearyl epoxide, (butane -2- yldeneaminos) epoxide, (diethylamino) epoxide, cyclohexyl epoxide, cyclooctyl epoxide, bicyclic [2.2.1] heptane -2- base epoxides, cyclononyl epoxide, (2- isopropyl -5- methylcyclohexyls) epoxide, (5- methyl -2- (propyl- 1- alkene -2- bases) cyclohexyl) epoxide, (octahydro -1H-4,7- Methanoindene -5- bases) epoxide, phenoxy group, p-methylphenyl epoxide, a tolyl epoxide, o-tolyl epoxide, adjacent carboxyphenoxy, Benzyl epoxide, benzene ethyoxyl, 3- phenyl-propoxies, cinnamyl epoxide, 1- phenyl-(2- ethyoxyl -2- oxos) ethyoxyl, (2- Methyl isophthalic acid-oxo -1- phenyl-propane -2- bases) epoxide, 2- ethyoxyl -2- oxo -1- (o-tolyl) ethyoxyls, 2- ethyoxyls - 1- (2- methoxyphenyls) -2- oxoethoxies, (4- ethyoxyl -4- oxo -1- phenyl but-2-ene -1- bases) epoxide, (1- benzene Formyl-cyclohexyl) epoxide and 2- hydroxyl-oxethyls.

The concrete example of the base that arbitrary hydrogen is replaced by fluorine be 3,3,3- trifluoro propyls, perfluoro capryl, 5,5,6,6,7, 7,8,8,8- nine fluoro- 4,4- double (trifluoromethyl) octyl group, 11- (perfluor phenoxy group) undecyl, 2,3,5,6- tetra- fluoro- 4- (three Methyl fluoride) phenyl, 3- phenoxy benzyls, 4 '-methoxyl group-[1,1 '-xenyl] -4- bases, 4- (octyl group epoxide) phenyl, fluorine methoxy Base, difluoro-methoxy, 2,2,2- trifluoro ethoxies, 2,2,2- trifluoroacetyl epoxides, 2,2,3,3- tetrafluoro propoxyl group, 2,2,3,3, Five fluorine propoxyl group of 3-, (1,1,1,3,3,3- HFC-236fa -2- bases) epoxide and perfluor phenoxy group.

In the base, the intermiscibility in the compositionss of comfortable compound is excellent, and the cured film for being formed the transparency and From the viewpoint of flatness is good, preferred base be methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, amyl group, Tertiary pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, 4- methylcyclohexyls, phenyl, benzyl, phenethyl, 4- isopropyls Base phenyl, sym-trimethylbenzene. base, 3,5- diethyl phenyls, 4- isobutyl phenenyls, 2,6- diethyl phenyls, acetoxy-methyl, 3- Methoxyl group -3- oxopropyls, 3- (2- methoxy ethoxy) propyl group, 4- methoxyl group -3,5- dimethyl benzyls, trimethyl silane Base, (TMS) methyl, 3- (TMS) propyl group, methoxyl group, ethyoxyl, propoxyl group, isopropoxy, propyl- 1- alkene -2- base epoxides, butoxy, tert-butoxy, sec-butoxy, isobutoxy, tertiary pentyl epoxide, hexyl epoxide, 2- ethyl fourths Epoxide, cyclohexyl epoxide, cyclooctyl epoxide, phenoxy group, p-methylphenyl epoxide, a tolyl epoxide, o-tolyl epoxide, benzyl Epoxide and 3- phenyl-propoxies, preferred base are methyl, ethyl, propyl group, phenyl, benzyl, acetoxy-methyl, trimethyl Silylation, (TMS) methyl, methoxyl group, ethyoxyl and propoxyl group.

R⁷In carbon number 1～26 organic group be also straight-chain alkyl, branch-like alkyl, cyclic alkyl, comprising ring-type alkane The alkyl of base, aromatic rings, the base comprising aromatic rings etc., the arbitrary methylene (CH of these bases₂) also can be by comprising O, NH, N Base or the base comprising Si replace, and, the arbitrary hydrogen of these bases also can be replaced by fluorine, but due to R⁷It is linked to O, therefore and R⁴、 R⁵And R⁶Compare, concrete example is restricted.

The concrete example of cyclic alkyl and the alkyl comprising cyclic alkyl is cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, 4- Methylcyclohexyl, bicyclic [2.2.1] heptane -2- bases, bicyclic [2.2.1] hept- 5- alkene -2- bases, 2- cyclohexyl-ethyls, 2- (rings Hex- 3- alkene -1- bases) ethyl, 2- cycloheptylethyls, 2- (bicyclic [2.2.1] hept- 5- alkene -2- bases) ethyl, 3- cyclohexyl third Base, 4- (tert-butyl group) cyclohexyl and adamantyl.

Arbitrary methylene (CH₂) by comprising O, N or Si base replace the base concrete example be acetoxy-methyl, 3- methoxyl group -3- oxopropyls, 3- (2- methoxy ethoxy) propyl group, 2,5,8, the 11- tetra- oxa- tetradecane -14- bases, 2,5,8, Tetra- oxa- heptadecane -17- bases of 11-, 11,11- dimethoxy undecyls, 2- (dimethylamino) ethyl, 2- (diethyl aminos Base) ethyl, tetrahydrofuran -3- bases, tetrahydrochysene -2H- pyrans -4- bases, 3- ((tetrahydrofuran -3- bases) methoxyl group) propyl group, 10- (1, 3- dioxolane -2- bases) decyl, 10- (1,3- diox -2- bases) decyl, morpholinyl, 4- methoxyl group -3,5- dimethyl Benzyl, hydroxymethyl, 2- hydroxyethyls, 3- hydroxypropyls, 1- carboxy ethyls, 4- hydroxybutyls, 4- hydroxyl -3- oxo butyl, TMS, (TMS) methyl, 3- (TMS) propyl group, 2- (2,4,4,6,6,8,8- seven methyl- 1,3,5,7- tetra- oxa- -2,4,6,8- tetra- silicon cyclooctane -2- bases) ethyl and 2- (dimethyl (phenyl) silylation) ethyl.

The concrete example of the base that arbitrary hydrogen is replaced by fluorine be 3,3,3- trifluoro propyls, perfluoro capryl, 5,5,6,6,7, 7,8,8,8- nine fluoro- 4,4- double (trifluoromethyl) octyl group, 11- (perfluor phenoxy group) undecyl, 2,3,5,6- tetra- fluoro- 4- (three Methyl fluoride) phenyl, 3- phenoxy benzyls, 4 '-methoxyl group-[1,1 '-xenyl] -4- bases and 4- (octyl group epoxide) phenyl.

In the base, the intermiscibility in the compositionss of comfortable compound is excellent, and the cured film for being formed the transparency and From the viewpoint of flatness is good, preferred base be methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, amyl group, Tertiary pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, 4- methylcyclohexyls, phenyl, benzyl, phenethyl, 4- isopropyls Base phenyl, sym-trimethylbenzene. base, 3,5- diethyl phenyls, 4- isobutyl phenenyls, 2,6- diethyl phenyls, acetoxy-methyl, 3- Methoxyl group -3- oxopropyls, 3- (2- methoxy ethoxy) propyl group, 4- methoxyl group -3,5- dimethyl benzyls, trimethyl silane Base, (TMS) methyl and 3- (TMS) propyl group, preferred base be methyl, ethyl, propyl group, phenyl, Benzyl, acetoxy-methyl, TMS and (TMS) methyl.

R⁴、R⁵、R⁶, and R⁷The organic group with epoxy radicals specifically oxirane -2- ylmethyls, 2- (oxa- rings third Alkane -2- bases) ethyl, 4- (oxirane -2- bases) butyl, 3- (oxirane -2- ylmethoxies) propyl group, 7- oxabicyclos [4.1.0] heptane -3- bases, 2- (7- oxabicyclos [4.1.0] heptane -2- bases) ethyl, dimethyl (4- (oxirane -2- bases Methoxyl group) butyl) silylation, 3- (7- oxabicyclos [4.1.0] heptane -3- bases) propyl group and 8- (oxirane -2- bases) be pungent Base.

In the base, from the viewpoint of the transparent and thermostability of the cured film for being formed certainly is good, preferred base is oxygen Heterocycle propane -2- ylmethyls, 2- (oxirane -2- bases) ethyl, 4- (oxirane -2- bases) butyl, 3- (oxa- rings third Alkane -2- ylmethoxies) propyl group, 7- oxabicyclos [4.1.0] heptane -3- bases and 2- (7- oxabicyclos [4.1.0] heptane -2- Base) ethyl, preferred base is oxirane -2- ylmethyls, 2- (oxirane -2- bases) ethyl, 4- (oxa- rings third Alkane -2- bases) butyl, 3- (oxirane -2- ylmethoxies) propyl group.

In formula (6), R⁸、R⁹、R¹⁰、R¹¹It is separately hydrogen or the organic group of carbon number 1～26, R¹²And R¹³It is only respectively It is on the spot hydrogen, the organic group of carbon number 1～26 or the organic group with epoxy radicals, R¹²And R¹³At least one be with epoxy radicals Organic group.N is more than 1 integer, R⁸Or R⁹Also can be from the R being bonded on different Si⁸、R⁹、R¹⁰, or R¹¹It is bonded and is formed Siloxanes ring, also, R¹⁰Or R¹¹Also can be from the R being bonded on different Si⁸、R⁹、R¹⁰, or R¹¹It is bonded and forms siloxanes ring.

R⁸～R¹³Carbon number 1～26 organic group and the organic group with epoxy radicals similarly can enumerate in the formula (5) R⁴、R⁵And R⁶In illustrated base, preferred base, preferred base are also identical.

The weight average molecular weight of the epoxide with siloxanes key knot position preferably 200～10,000, it is more excellent Elect 200～5,000 as.If being in these scopes, flatness becomes good.Therefore, the value of the m in the formula (5) is preferably 2 The value of～50, more preferably 2～25, the n in the formula (6) is preferably 1～74, more preferably 1～36.

Epoxide with siloxanes key knot position is in the not epoxide with siloxanes key knot position and tool Have siloxanes key knot position epoxide total amount in ratio be 0.5 weight %～70 weight %, preferably 1 weight Amount %～50 weight %.If being in these scopes, flatness, the transparency, thermostability and viscosity (tackiness) it is flat Weighing apparatus becomes good.

The concrete example of the epoxide with siloxanes key knot position is with epoxy radicals and cannot be by further Condensation and produce the organo-silicon compound of siloxanes key；One kind of siloxanes key can be produced with epoxy radicals and by condensation The copolymer of organo-silicon compound above；Or one kind of siloxanes key can be produced with the epoxy radicals and by condensation More than organo-silicon compound and the not organo-silicon compound with epoxy radicals of siloxanes key can be produced by condensation be total to Polymers.If commercially available product, then can enumerate：1,3- double [2- (3,4- expoxycyclohexyl) ethyl] tetramethyl disiloxane (business The name of an article；The manufacture of prompt Leicester's technical concern company limited (Gelest Technologies Incorporated)), TSL9906 (trade name；Figure new high-tech material (Momentive Performance Material) (stock) advanced in years manufacture), Kao Teao West Roads (CoatOsil) MP-200 (trade names；Figure new high-tech material (stock) advanced in years manufacture), sky Po Sailang (Conpoceran) SQ506 (commodity Name；Waste river chemistry (stock) manufacture), ES-1023 (trade names；SHIN-ETSU HANTOTAI's chemical industry (stock) is manufactured) etc..

1-2-2. does not have the epoxide of siloxanes key knot position

As long as the not epoxide with siloxanes key knot position used in the present invention and the heat for forming the present invention The intermiscibility of the other compositions of curable adhensive compositions is good, then be not particularly limited, and can enumerate：Diglycidyl ether type epoxy resin, Glycidyl ester type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol-A phenolic Type epoxy resin, aliphatic polyglycidyl ether compound or ring type aliphatic epoxy resin, the monomer with epoxy radicals Polymer and the monomer with epoxy radicals and other monomers copolymer etc..

Diglycidyl ether type epoxy resin can be enumerated：Tyke not (TECHMORE) VG3101L (trade names；General woods Tyke (Printec) limited company), EHPE-3150 (trade names；Daicel (Daicel) limited company), EPPN- 501H, EPPN-502H (are trade name；NIPPON PHARMACEUTICAL CO., LTD), JER 1032H60 (trade names；Mitsubishi Chemical's stock Part company limited) etc..Glycidyl ester type epoxy resin can be enumerated：Pellet receives Cauer (Denacol) EX-721 (trade names；Length is rapids Chemical conversion (Nagase ChemteX) limited company), 1,2- cyclohexane dicarboxylic acid 2-glycidyl ester (trade names；Tokyo Manufacture into Industries, Inc), phenol novolak type epoxy resin can be enumerated：EPPN-201 (trade names；Japanese chemical medicine Limited company), JER 152, JER 154 (are trade name；Limited company of Mitsubishi Chemical) etc..Cresol novolak Type epoxy resin can be enumerated：EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (are trade name；Japanese chemical medicine Limited company) etc..Phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin can be enumerated：JER 157S65, JER 157S70 (are commodity Name；Limited company of Mitsubishi Chemical) etc..Ring type aliphatic epoxy resin can be enumerated：Sai Luo West Germany (Celloxide) 2021P, Sai Luo West Germany (Celloxide) 3000 (is trade name；Daicel (Daicel) limited company) etc..

1-3. epoxy curing agent

In the thermosetting compositionss of the present invention, in order that flatness, chemical-resistant are improved, epoxy is it is also possible to use hard Agent.Epoxy curing agent there are anhydride system sclerosing agent, amine system sclerosing agent, phenol system sclerosing agent, imidazoles system sclerosing agent, catalyst type Thermonasty acid producing agent such as sclerosing agent and sulfonium salt, benzothiazolium salt, ammonium salt, phosphonium salts etc., avoids the coloring of cured film and hard certainly From the viewpoint of changing the thermostability of film, preferred anhydrides system sclerosing agent or imidazoles system sclerosing agent.

The concrete example of anhydride system sclerosing agent can enumerate aliphatic dicarboxylic acid acid anhydride (such as maleic anhydride, tetrahydrophthalic acid Acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydro trimellitic anhydride etc.), aromatic polycarboxylic acid acid anhydride (such as phthalic anhydride, trimellitic anhydride etc.), styrene-maleic anhydride copolymer.In these anhydride system sclerosing agents preferably The thermostability trimellitic anhydride good with the deliquescent balance to solvent and hexahydro trimellitic anhydride.

The concrete example of imidazoles system sclerosing agent can enumerate 2- undecyl imidazoles, 2- heptadecyl imidazoles, 2- phenylimidazoles, 2- Phenyl -4-methylimidazole, 2,3- dihydro -1H- pyrrolo-es [1,2-a] benzimidazoles, 1- cyano ethyl -2- undecyl imidazoles Trimellitate.The preferred hardening 2- undecyl good with the deliquescent balance to solvent in these imidazoles system sclerosing agents Imidazoles.

The ratio of the acid of 1-4. polyesteramides, epoxide and epoxy curing agent

Relative to polyesteramide 100 weight portions of acid in the thermosetting compositionss of the present invention, the total amount of epoxide Ratio be 20 weight portion～400 weight portions.It is if the ratio of the total amount of epoxide is the scope, flatness, heat-resisting Property, chemical-resistant, adhesion balance it is good.The total amount of epoxide is preferably the model of 50 weight portion～300 weight portions Enclose.

In the thermosetting compositionss of the present invention, in the case of using epoxy curing agent, relative to epoxide 100 weight portions, the ratio of epoxy curing agent is 0.1 weight portion～60 weight portion.It is anhydride system sclerosing agent with regard to epoxy curing agent In the case of addition, more specifically, preferably with the acid anhydride or carboxylic for epoxy radicals, in epoxy curing agent Base becomes the mode of 0.1 times of equivalent～1.5 times equivalent and is added.Now, acid anhydride is calculated with bivalence.If with into Mode for 0.15 times of equivalent～0.8 times equivalent adds acid anhydride or carboxyl, then chemical-resistant is further improved, therefore more It is preferred that.

1-5. other compositions

In the thermosetting compositionss of the present invention, various additives can be added to improve coating homogeneity, cementability.Addition Agent can mainly be enumerated：Solvent, the levelling agent/surfactant of anion system, cation system, nonionic system, fluorine system or silicon systems, silicon The antioxidants such as the adhesion elevator such as alkane coupling agent, hindered phenol series, amine system of being obstructed, phosphorus system, chalcogenide compound.

1-5-1. solvent

Solvent can also be added in the thermosetting compositionss of the present invention.In the thermosetting compositionss of the present invention, institute is any The solvent of addition preferably can dissolve the solvent of described polyesteramide acid, epoxide, epoxy curing agent etc..The tool of the solvent Style is methanol, ethanol, 1- propanol, 2- propanol, n-butyl alcohol, 2- butanol, isobutanol, the tert-butyl alcohol, acetone, 2-butanone, acetic acid second Ester, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, hydroxy methyl acetate, hydroxyl ethyl acetate, hydroxyacetic acid fourth Ester, methoxy menthyl acetate, ethyl methoxyacetate, 2-Methoxyacetic acid butyl ester, ethoxy acetate, ethoxyacetic acid second Ester, 3- epoxide methyl propionates, 3- hydroxypropionates, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxy-cs Sour methyl ester, 3- ethoxyl ethyl propionates, 2 hydroxy propanoic acid methyl ester, 2 hydroxy propanoic acid propyl ester, 2- methoxy methyl propionates, 2- methoxies Base ethyl propionate, 2- methoxy propyl propyl propionates, 2- ethoxypropanoates, 2- ethoxyl ethyl propionates, 2- hydroxy-2-methyls third Sour methyl ester, 2- hydroxy-2-methyl ethyl propionates, 2- methoxyl groups -2 Methylpropionic acid methyl ester, 2- ethyoxyls -2 Methylpropionic acid ethyl ester, Methyl pyruvate, ethyl pyruvate, Propyl 2-oxopropionate, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid methyl ester, 2- Oxobutyric, 4- hydroxy-4-methyl-2-pentanones, ethylene glycol, diethylene glycol, triethylene glycol, Propylene Glycol, dipropylene glycol, three Propylene Glycol, BDO, glycol monoethyl ether, ethylene glycol monoethyl ether, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, the third two Alcohol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetass, ethylene glycol only son Ether acetic acid ester, Ketocyclopentane, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetass, diethylene glycol monoethyl ether, diethylene glycol list Ether acetate, diethylene glycol monobutyl ether, butyl carbitol acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol methyl ethyl ether, tetrahydrofuran, acetonitrile, dioxs, toluene, dimethylbenzene, gamma-butyrolacton or N, N- dimethyl Acetamide and Ketohexamethylene.Solvent can be one kind of these solvents, may also be the two or more mixture of these solvents.

1-5-2. surfactant

In the thermosetting compositionss of the present invention, can also add surfactant to improve coating homogeneity.Live on surface The concrete example of property agent can enumerate Pohle not Lip river (Polyflow) No.45, Pohle not Lip river (Polyflow) KL-245, Pohle not Lip river (Polyflow) No.75, Pohle not Lip river (Polyflow) No.90, Pohle not Lip river (Polyflow) No.95 (is commodity above Name；Common prosperity society chemistry limited company), Di Sipabike (Disperbyk) 161, Di Sipabike (Disperbyk) 162, Di Sipabike (Disperbyk) 163, Di Sipabike (Disperbyk) 164, Di Sipabike (Disperbyk) 166, enlightening Si Pabike (Disperbyk) 170, Di Sipabike (Disperbyk) 180, Di Sipabike (Disperbyk) 181, Di Si Pa Bike (Disperbyk) 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346, BYK361N, BYK-UV3500, BYK-UV3570 (are trade name above；Japanese Bi Ke chemistry (BYK Chemie Japan) stock Part company limited), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (be trade name above；SHIN-ETSU HANTOTAI Learn Industries, Inc), Sha Fulong (Surflon) SC-101, Sha Fulong (Surflon) KH-40, Sha Fulong (Surflon) S611 (is trade name above；AGC beautifies clearly (AGC Seimi Chemical) limited company), good fortune Ji Te (Ftergent) 222F, Fu Jite (Ftergent) 208G, Fu Jite (Ftergent) 251, Fu Jite (Ftergent) 710FL, Fu Jite (Ftergent) 710FM, Fu Jite (Ftergent) 710FS, Fu Jite (Ftergent) 601AD, Fu Ji Spy (Ftergent) 602A, Fu Jite (Ftergent) 650A, FTX-218 (are trade name above；Ni Aosi (Neos) share Company limited), Ai Futuo (EFTOP) EF-351, Ai Futuo (EFTOP) EF-352, Ai Futuo (EFTOP) EF-601, Ai Futuo (EFTOP) EF-801, Ai Futuo (EFTOP) EF-802 (is trade name above；Mitsubishi Materials (Mitsubishi Material) limited company), Mei Jiafa (Megafac) F-171, Mei Jiafa (Megafac) F-177, Mei Jiafa (Megafac) F-410, Mei Jiafa (Megafac) F-430, Mei Jiafa (Megafac) F-444, Mei Jiafa (Megafac) F- 472SF, Mei Jiafa (Megafac) F-475, Mei Jiafa (Megafac) F-477, Mei Jiafa (Megafac) F-552, Mei Jiafa (Megafac) F-553, Mei Jiafa (Megafac) F-554, Mei Jiafa (Megafac) F-555, Mei Jiafa (Megafac) F- 556th, Mei Jiafa (Megafac) F-558, Mei Jiafa (Megafac) F-559, Mei Jiafa (Megafac) R-30, Mei Jiafa (Megafac) R-94, Mei Jiafa (Megafac) RS-75, Mei Jiafa (Megafac) RS-72-K, Mei Jiafa (Megafac) RS- 76-NS, Mei Jiafa (Megafac) DS-21 (is trade name above；Di Aisheng (DIC) limited company), Di Gaotun (TEGO Twin) 4000, Di Gaotun (TEGO Twin) 4100, Di Gaofuluo (TEGO Flow) 370, Di Gaoge Riders (TEGO Glide) the 420, high rad (TEGO of Di Gaoge Riders (TEGO Glide) 440, Di Gaoge Riders (TEGO Glide) 450, enlightening Rad) the high rad of 2200N, enlightening (TEGO Rad) 2250N (is trade name, Japan wins wound Degussa (Evonik- above Degussa Japan) limited company), fluoroalkyl benzene sulfonate, fl muoroalkyl's salt, fluoroalkyl polyoxyethylene ether, halothane Base ammonium iodide, fluoroalkyl glycine betaine, fluoroalkyl sulfonate, two glycerol four (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium Salt, fluoroalkyl sulfamate, ethylene nonyl phenyl ether, NONIN HS 240, polyoxyethylene alkyl ether, polyoxy Ethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl base ether, Polyethylene oxide are hard Aliphatic radical ether, polyoxyethylene laurate, polyoxyethylene oleate, Myrj 45, polyoxyethylene laural base amine, Pyrusussuriensiss Alcohol acid anhydride laurate, sorbitol anhydride cetylate, sorbitan tristearate, sorbitan oleate, sorbitan fatty acid Ester, polyoxyethylene sorbitol acid anhydride laurate, polyoxyethylene sorbitol acid anhydride cetylate, polyoxyethylene sorbitol acid anhydride stearic acid Ester, polyoxyethylene sorbitol acid anhydride oleate, Polyethylene oxide naphthyl ether, alkylbenzenesulfonate and alkyl diphenyl base ether disulfonate. Preferably use at least one in these compounds.

In these surfactants, if selected from BYK306, BYK342, BYK346, KP-341, KP-358, KP-368, Sha Fulong (Surflon) S611, Fu Jite (Ftergent) 710FL, Fu Jite (Ftergent) 710FM, Fu Jite (Ftergent) 710FS, Fu Jite (Ftergent) 650A, Mei Jiafa (Megafac) F-477, Mei Jiafa (Megafac) F- 556th, Mei Jiafa (Megafac) RS-72-k, Di Gaotun (TEGO Twin) 4000, fluoroalkyl benzene sulfonate, fl muoroalkyl's salt, In fluoroalkyl polyoxyethylene ether, fluoroalkyl sulfonate, fluoroalkyl leptodactyline and fluoroalkyl sulfamate at least one Kind, then the coating homogeneity of thermosetting compositionss is uprised, therefore preferably.

The content of the surfactant in the thermosetting compositionss of the present invention is preferably with respect to thermosetting compositionss Total amount and be 0.01 weight %～10 weight %.

1-5-3. adhesion elevators

From from the viewpoint of making adhesion of the formed cured film with substrate further improve, the thermosetting of the present invention Compositionss can also further contain adhesion elevator.

This kind of adhesion elevator can for example use the coupling agent of silane system, aluminum system or titanate esters system.Can specifically arrange Lift 3- glycidoxypropyl dimethylethoxysilanes, 3- glycidoxypropyl diethoxy silanes, 3- contractings Water glycerol epoxide propyl trimethoxy silicane (such as Sa Laaisi (Sila-Ace) S510；Trade name；The limited public affairs of JNC shares Department), 2- (3,4- expoxycyclohexyl) ethyl trimethoxy silane (such as Sa Laaisi (Sila-Ace) S530；Trade name； JNC limited companies), 3-mercaptopropyi trimethoxy silane (such as Sa Laaisi (Sila-Ace) S810；Trade name；JNC Limited company) etc. silane series coupling agent, the aluminium system coupling agent such as acetyl alkoxyl aluminum-diisopropoxide and tetra isopropyl double (two Octyl group phosphite ester) the titanate esters system coupling agent such as titanate esters.

In these adhesion elevators, 3- glycidoxypropyls triethoxysilane is due to making the effect that adhesion is lifted It is really big and preferred.

The content of adhesion elevator is below 10 weight % preferably with respect to thermosetting total composition.The opposing party It is more than face, preferably 0.01 weight %.

1-5-4. antioxidant

From the viewpoint of picking up by oneself high transparent, preventing cured film exposure xanthochromia in the event of high temperatures, the heat of the present invention Curable adhensive compositions can also further contain antioxidant.

Hindered phenol series, amine system of being obstructed, phosphorus system, chalcogenide compound etc. can also be added to resist in the thermosetting compositionss of the present invention Oxidant.Wherein, from from the viewpoint of weatherability, preferred hindered phenol series.Concrete example can enumerate Yi Lu Jia Nuosi (Irganox) 1010th, Yi Lu Jia Nuosi (Irganox) FF, Yi Lu Jia Nuosi (Irganox) 1035, Yi Lu Jia Nuosi (Irganox) 1035FF, Easily fine jade Jia Nuosi (Irganox) 1076, Yi Lu Jia Nuosi (Irganox) 1076FD, Yi Lu Jia Nuosi (Irganox) 1076DWJ, Easy fine jade Jia Nuosi (Irganox) 1098, Yi Lu Jia Nuosi (Irganox) 1135, Yi Lu Jia Nuosi (Irganox) 1330, Yi Lu Good Northey (Irganox) 1726, Yi Lu Jia Nuosi (Irganox) 1425WL, Yi Lu Jia Nuosi (Irganox) 1520L, Yi Lujia Northey (Irganox) 245, the good promise of Yi Lu Jia Nuosi (Irganox) 245FF, Yi Lu Jia Nuosi (Irganox) 245DWJ, Yi Lu This (Irganox) 259, Yi Lu Jia Nuosi (Irganox) 3114, Yi Lu Jia Nuosi (Irganox) 565, Yi Lu Jia Nuosi (Irganox) 565DD, Yi Lu Jia Nuosi (Irganox) 295 (is trade name；Japanese BASF (BASF Japan) share has Limit company), Ai Di Coase tower ripple (ADK STAB) AO-20, Ai Di Coase tower ripple (ADK STAB) AO-30, Ai Di Coase tower ripples (ADK STAB) AO-50, Ai Di Coase tower ripple (ADK STAB) AO-60, Ai Di Coase tower ripple (ADK STAB) AO-70, Ai Di Coase tower ripple (ADK STAB) AO-80 (is trade name；Ai Dike (ADEKA) limited company).Wherein more preferably easy fine jade Good Northey (Irganox) 1010, Ai Di Coase tower ripple (ADK STAB) AO-60.

Relative to the total amount of thermosetting compositionss, add the antioxidant of 0.1 weight portion～5 weight portion and use.

1-5-7. other additives

In the case where polyesteramide acid does not contain styrene-maleic anhydride copolymer as raw material, can also add benzene Ethylene maleic acid anhydride copolymer is used as other compositions.

The preservation of 1-6. thermosetting compositionss

If the thermosetting compositionss of the present invention are preserved in the range of -30 DEG C～25 DEG C, steady during the Jing of compositionss It is qualitative to become good and preferred.If storage temperature is -20 DEG C～10 DEG C, also without precipitate more preferably.

2. the cured film by obtained by thermosetting compositionss

The thermosetting compositionss of the present invention can be obtained in the following way：By polyesteramide acid, with siloxanes key The epoxide of knot position, the not epoxide with siloxanes key knot position and epoxy curing agent are mixed, according to Target property, further optionally selectivity addition solvent, coupling agent, surfactant and other additives, these are changed Compound equably mixed dissolution.

If will as mentioned above and prepare thermosetting compositionss (and in the case of solvent-free solid state, dissolving After in a solvent) it is coated on matrix surface, solvent is removed for example, by heating etc., then can form film.In matrix Surface coated heat curable adhensive compositions can be using the existing known side such as spin-coating method, rolling method, infusion process and slot coated method Method.Secondly, (prebake conditions) are heated to the film using heating plate (hot plate) or baking oven (oven) etc..Heating condition It is different because of the species and allotment ratio of each composition, generally at 70 DEG C～150 DEG C, it is 5 minutes～15 points if using baking oven Clock, is 1 minute～5 minutes if using heating plate.Thereafter, in order that film hardening, can obtain hard by heat treated Change film, the heat treated be at 180 DEG C～250 DEG C, preferably 200 DEG C～250 DEG C, if baking oven then carry out 30 minutes～ 90 minutes, if heating plate then carries out 5 minutes～30 minutes.

As mentioned above and the cured film of gained in heating, 1) the partially dehydrated cyclisation of the polyamic acid of polyesteramide acid and shape Into imide bond, 2) carboxylic acid of polyesteramide acid is reacted and molecular weight with epoxide, and 3) epoxide hardening And molecular weight, it is therefore very tough, and the transparency, thermostability, chemical-resistant, flatness, adhesion, light resistance and Resistant sputtering is excellent.Therefore, cured film of the invention is effective if the protecting film as colored filter, can use the colour Optical filter is manufacturing liquid crystal display cells or solid-state imager.And, in addition to the protecting film of colored filter, this If bright cured film as the transparent insulating film being formed between TFT and transparency electrode or be formed in transparency electrode and alignment films it Between transparent insulating film it is then effective.Even if in addition, protecting film of the cured film of the present invention as LED illuminator is also effective.

[embodiment]

Secondly, the present invention is illustrated by synthesis example, reference example, embodiment and comparative example, but the present invention is simultaneously Any restriction of these embodiments is not received.First, synthesis includes tetracarboxylic dianhydride, diamidogen, multi-hydroxy compound as shown below Product polyesteramide acid solution (synthesis example 1, synthesis example 2, synthesis example 3, and synthesis example 4).

The synthesis of [synthesis example 1] polyesteramide acid solution (A1)

In the four-hole boiling flask with blender, being loaded with following weight has carried out the 3- methoxypropionic acid first of dehydration and purification Ester (methyl 3-methoxy propionate, be slightly designated as " MMP " below), 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride (3,3 ', 4,4 '-diphenylether tetracarboxylic dianhydride, be slightly designated as " ODPA " below), Isosorbide-5-Nitrae-fourth Glycol, benzylalcohol, flow down in drying nitrogen, carry out 3 hours stirring at 130 DEG C.

Thereafter, reactant liquor is cooled to into 25 DEG C, with following weight input 3,3 '-diamino diphenyl sulfone (diamino Diphenyl sulfone, are slightly designated as " DDS " below), MMP, carry out at 20 DEG C～30 DEG C 2 hours stirring after, at 115 DEG C Carry out 1 hour stirring.

DDS 29.33g

MMP 183.04g

[Z/Y=3.0, (Y+Z)/X=0.8]

Solution is cooled to into room temperature, 30 weight % solution (A1) of the polyesteramide acid of pale yellow transparent are obtained.To solution A part be sampled, the gravimetry mean molecule quantity using gpc analysis (polystyrene standard).As a result, gained The weight average molecular weight of polymer (A1) is 4,200.

The synthesis of [synthesis example 2] polyesteramide acid solution (A2)

In the four-hole boiling flask with blender, sequentially being loaded with following weight has carried out the Propylene Glycol list first of dehydration and purification Ether acetic acid ester (propylene glycol monomethyl ether acetate, be slightly designated as " PGMEA " below), 1,2,3, 4- butane tetracarboxylic acid dianhydrides (being slightly designated as " BT-100 " below), SMA1000P (trade names；Styrene-maleic anhydride copolymer, river Crude oil limited company), BDO, benzylalcohol, flow down in drying nitrogen, carry out 3 hours stirring at 125 DEG C.

Thereafter, reactant liquor is cooled to into 25 DEG C, DDS, PGMEA are put into following weight, 2 is carried out at 20 DEG C～30 DEG C little When stirring after, carry out at 125 DEG C 2 hours stir.

DDS 9.60g

PGMEA 36.00g

[Z/Y=2.7, (Y+Z)/X=0.9]

Solution is cooled to into room temperature, 30 weight % solution (A2) of the polyesteramide acid of pale yellow transparent are obtained.To solution A part be sampled, the gravimetry mean molecule quantity using gpc analysis (polystyrene standard).As a result, gained The weight average molecular weight of polymer (A2) is 10,000.

The synthesis of [synthesis example 3] polyesteramide acid solution (A3)

In the four-hole boiling flask with blender, sequentially being loaded with following weight has carried out PGMEA, BT- of dehydration and purification 100th, SMA1000P, BDO, benzylalcohol, flow down in drying nitrogen, carry out 3 hours stirring at 125 DEG C.

DDS 3.14g

PGMEA 36.00g

[Z/Y=8.0, (Y+Z)/X=0.8]

Solution is cooled to into room temperature, 30 weight % solution (A3) of the polyesteramide acid of pale yellow transparent are obtained.To solution A part be sampled, using gpc analysis (polystyrene standard) gravimetry mean molecule quantity.As a result, gained is poly- The weight average molecular weight of compound (A3) is 9,000.

The synthesis of [synthesis example 4] polyesteramide acid solution (A4)

In the four-hole boiling flask with blender, sequentially being loaded with following weight has carried out PGMEA, the diethyl of dehydration and purification Glycol methyl ethyl ether (diethylene glycol methyl ethyl ether, be slightly designated as " EDM " below), ODPA, SMA1000P, BDO, benzylalcohol, flow down in drying nitrogen, carry out 3 hours stirring at 120 DEG C.

Thereafter, reactant liquor is cooled to into 25 DEG C, DDS, MMP are put into following weight, 2 hours is carried out at 20 DEG C～30 DEG C After stirring, carry out 2 hours stirring at 120 DEG C.

DDS 12.72g

EDM 29.68g

[Z/Y=2.0, (Y+Z)/X=1.0]

Solution is cooled to into room temperature, 30 weight % solution (A4) of the polyesteramide acid of pale yellow transparent are obtained.To solution A part be sampled, using gpc analysis (polystyrene standard) gravimetry mean molecule quantity.As a result, gained is poly- The weight average molecular weight of compound (A4) is 21,000.

Secondly, synthesize as shown below by with epoxy radicals and one kind of siloxanes key can be produced by condensation with On the copolymer that obtained for material composition is reacted of organo-silicon compound be used as the ring with siloxanes key knot position Oxygen compound (synthesis example 5, and synthesis example 6).

The synthesis of the epoxide of [synthesis example 5] with siloxanes key knot position (S1)

In the four-hole boiling flask of 1000ml, loading carried out the toluene 109.24g of dehydration and purification, purified water 21.62g and (tetramethylammonium hydroxide, are slightly designated as the tetramethyl ammonium hydroxide aqueous solution of 25 weight % concentration below " TMAH ") 2.92g, and start stirring.Additionally, in the cylindrical shape addition funnel of 300ml, loading has carried out the first of dehydration and purification Benzene 53.78g, Sa Laaisi (Sila-Ace) S510 (trade names；JNC (stock) is manufactured, and is slightly designated as " S510 " below) 94.54g As dropping liquid, and after lasting in the four-hole boiling flask that total amount is flowed into the 1000ml for being incorporated with raw material for 1 hour, carry out 2 Hour is stirred and is condensed.A point liquid is carried out to reactant liquor using purified water, using rotary evaporator from the organic layer of gained Toluene is distilled off, the epoxide with siloxanes key knot position (S1) is derived from.The utilization GPC of the solution and determine Weight average molecular weight be 3,200 (polystyrene conversions).

The synthesis of the epoxide of [synthesis example 6] with siloxanes key knot position (S2)

In the four-hole boiling flask of 1000ml, loading carried out the toluene 137.64g of dehydration and purification, purified water 32.44g and Tetramethyl ammonium hydroxide aqueous solution (being slightly designated as " TMAH " below) 4.38g of 25 weight % concentration, and start stirring.Additionally, In the cylindrical shape addition funnel of 300ml, loading has carried out toluene 67.76g, Sa Laaisi (Sila-Ace) of dehydration and purification S51028.36g, phenyltrimethoxysila,e 59.48g, trimethylmethoxysilane 31.26g are used as dropping liquid, and last 1 After total amount is flowed in the four-hole boiling flask of the 1000ml for being incorporated with raw material by hour, carry out stirring in 2 hours and be condensed. A point liquid is carried out to reactant liquor using purified water, toluene is distilled off from the organic layer of gained using rotary evaporator, is thus obtained There must be the epoxide (S2) of siloxanes key knot position.The utilization GPC of the solution and the weight average molecular weight that determines are 1,900 (polystyrene conversions).

Secondly, synthesize as shown below by with the monomer with epoxy radicals and and the monomer carry out other of copolymerization The copolymer obtained for material composition is reacted by monomer is used as the not epoxide with siloxanes key knot position and (closes Into example 7, and synthesis example is 8).

[synthesis example 7] does not have the synthesis of the epoxide solution (E1) of siloxanes key knot position

In the four-hole boiling flask of the 1000ml with thermometer, blender, material pouring inlet and nitrogen inlet, load into Gone dehydration and purification MMP 300.00g, (glycidyl methacrylate, slightly remember glycidyl methacrylate below For " GMA ") 160.00g, butyl methacrylate (butyl methacrylate are slightly designated as " BMA " below) 40.00g, conduct The 2 of polymerization initiator, double (2, the 4- methyl pentane nitrile) 8.00g of 2 '-azo carry out 2 hours heating under 90 DEG C of polymerization temperature And be polymerized.The not epoxide 40 with siloxanes key knot position is obtained by reactant liquor is cooled to less than 30 DEG C Weight % solution (E1).The utilization GPC of the solution and the weight average molecular weight that determines is 78,000 (polystyrene conversions).

[synthesis example 8] does not have the synthesis of the epoxide solution (E2) of siloxanes key knot position

In the four-hole boiling flask of the 1000ml with thermometer, blender, material pouring inlet and nitrogen inlet, load into The MMP 420.00g of dehydration and purification, glycidyl methacrylate 162.00g, dimethacrylate are gone 18.00g, as the 2 of polymerization initiator, double (2,4- methyl pentane nitrile) 27.00g of 2 '-azo, under 110 DEG C of polymerization temperature Carry out heating in 2 hours and be polymerized.Obtained by reactant liquor is cooled to less than 30 DEG C and there is no siloxanes key knot position 30 weight % solution (E2) of epoxide.The utilization GPC of the solution and the weight average molecular weight that determines is 3,600 (poly- Styrene converts).

Secondly, using synthesis example 1, synthesis example 2, synthesis example 3, and synthesis example 4 in gained polyesteramide acid (A1, A2, A3 and A4)；Synthesis example 5, and synthesis example 6 in gained the epoxide with siloxanes key knot position；Synthesis example 7, and close The not epoxide with siloxanes key knot position of gained in example 8；Commercially available epoxy resin (has siloxanes key knot The epoxide of position or the not epoxide with siloxanes key knot position)；And epoxy curing agent, prepare as shown below Thermosetting compositionss.Cured film is obtained by the thermosetting compositionss, the evaluation (1～reality of embodiment of the cured film is carried out Apply example 11, and 1～comparative example of comparative example is 6).

[embodiment 1]

Nitrogen displacement is carried out to the detachable flask of the 500ml with agitator, in the flask, loads synthesis example 1 Polyesteramide acid solution (A1) 100.00g of middle gained, as with siloxanes key knot position epoxide Kao Teao West Road (CoatOsil) MP-200 (being slightly designated as " S3 " below) 1.50g, as not with siloxanes key knot position epoxy compound The Tyke of thing not (TECHMORE) VG3101L (trade names；General woods Tyke (Printec) (stock), is slightly designated as " E3 " below) 58.50g, trimellitic anhydride (being slightly designated as " TMA " below) 6.00g as epoxy curing agent, as the Ai Di Coases of additive Tower ripple (ADK STAB) AO-60 (trade names；Ai Dike (ADEKA) (stock) is manufactured) it is 0.48g, pure as the carrying out dehydration of solvent The MMP 367.38g and EDM 109.34g of change, carry out 3 hours stirring so as to equably dissolve at room temperature.Secondly, input is beautiful Good method (Megafac) F-556 (trade names；Di Aisheng (DIC) (stock) is manufactured) 0.17g, carry out at room temperature 1 hour stirring, use Aperture is that 0.2 μm of membrane filter is filtered and prepared coating fluid.

Secondly, with 800rpm last 10 seconds by the coating fluid be spun on glass substrate and on colored filter substrate after, Film is formed so that 80 DEG C carry out 3 minutes prebake conditions on hot plate.Thereafter, carry out 30 minutes heating with 230 DEG C in an oven, Thus make film hardening and obtain the cured film that thickness is 1.0 μm.

With regard to the cured film for obtaining in this way, spy is evaluated with regard to the transparency, light resistance, flatness and thermostability Property.

[evaluation methodology of the transparency]

In the glass substrate with cured film of gained, with UV, visible light near infrared spectrometer (trade name；V- 670th, Japanese light splitting (stock) manufacture) wavelength that determines only cured film is the absorbance under the light of 400nm.By absorbance be 97% with On situation be evaluated as "○", the situation less than 97% is evaluated as into "×".

[sunproof evaluation methodology]

For the glass with cured film after being evaluated to the transparency in [evaluation methodology of the transparency] Glass substrate, with ultraviolet and ozone cleaning device (trade name；PL2003N-12, light source；Low pressure mercury lamp, SEN special light sources (stock) Manufacture) carry out 1J/cm²The ultraviolet and ozone of (254nm conversions) is processed, after carrying out heating in 30 minutes in an oven, with 230 DEG C, With UV, visible light infrared spectrophotometer (trade name；V-670, Japanese light splitting (stock) manufacture) wavelength that determines only cured film is Absorbance under the light of 400nm.The situation that absorbance is more than 95% is evaluated as into "○", the situation less than 95% is evaluated as “×”。

[evaluation methodology of flatness]

Device (trade name is determined with jump/surface roughness/fine shape；P-15, KLA-Tencor (KLA TENCOR) share have Limit company) determine gained the colored filter substrate with cured film cured film surface jump.Will be comprising black matrix" R, G, B pixel between the situation of (being slightly designated as " maximum jump " below) less than 0.25 μm maximum of jump be evaluated as "○", More than 0.25 μm of situation is evaluated as into "×".And, the colored filter substrate for being used is making for about 0.5 μm of maximum jump With the pigment self-dispersible color optical filter (color filter are slightly designated as " CF " below) of resin black matrix.

[evaluation methodology of thermostability]

After the glass substrate with cured film of gained is carried out reheating for 1 hour at 230 DEG C, the film before heating is determined Thickness after thick and heating, calculates residual film ratio with following calculating formulas.The measure of thickness using the jump/surface roughness/ Fine shape determines device (trade name；P-15, KLA-Tencor (KLA TENCOR) limited company).By the residual film ratio after heating it is More than 96% situation is evaluated as "○", and situation of the residual film ratio after heating less than 96% is evaluated as "×".

Residual film ratio=(thickness before thickness/heating after heating) × 100

[evaluation methodology of viscosity]

After 10 seconds being lasted with 800rpm the coating fluid being spun on glass substrate, carry out 3 with 80 DEG C on hot plate Minute prebake conditions and form film.Thereafter, the presence or absence of pleat (tuck) is judged by palpation.The film after prebake conditions will be touched, And "○" is evaluated as in situation of the film surface without visual change of shape, the situation for having change of shape is evaluated as into "×".

[2～embodiment of embodiment 11]

According to the method for embodiment 1, with ratio (unit described in table 1-1 and table 1-2：G) each composition is mixed into molten Solve and obtain thermosetting compositionss.In addition, the abbreviation of each compound in regard to table, S4 is denoted as being bonded with siloxanes Double [2- (3, the 4- expoxycyclohexyl) ethyl] tetramethyl disiloxane (trade names of 1,3- of the epoxide at position；Jie Lai This trick limited company (Gelest Technologies Incorporated) manufactures).The S510 tables on additive hurdle Show adhesion elevator Sa Laaisi (Sila-Ace) S510 (trade names；JNC limited companies), AO-60 represents antioxidation Agent Ai Di Coase tower ripple (ADK STAB) AO-60 (trade names；Ai Dike (ADEKA) (stock) is manufactured), F-556 represents surface activity Agent Mei Jiafa (Megafac) F-556 (trade names；Di Aisheng (DIC) (stock) is manufactured).

[1～comparative example of comparative example 6]

According to the method for embodiment 1, with ratio (unit described in table 2：G) each composition mixed dissolution is obtained into heat Curable adhensive compositions.

And, the evaluation result of the cured film of 1～embodiment of embodiment 11 is collected and is recorded in table 1-1 and table 1-2, will The evaluation result of the cured film of 1～comparative example of comparative example 6 collects and is recorded in table 2.

Table 1-1

Table 1-2

Table 2

Result according to table 1：1～embodiment of embodiment 11 has used the ring with siloxanes key knot position The flatness of the cured film of oxygen compound is excellent, obtains balance at all aspects of the transparency, light resistance and thermostability.

On the other hand, although the cured film that only used epoxide of comparative example 1 and comparative example 5 and comparative example 6 The transparency, excellent heat resistance, but flatness is poor.The E3 used in epoxide of comparative example 2, and with less than preferred scope In the case of amount is using the epoxide with siloxanes key knot position, although being the transparency, light resistance and excellent heat resistance, But the result of flatness difference.Opposite to that, the amount to be more than preferred scope of comparative example 3 and comparative example 4 is used with siloxanes In the case of the epoxide at bond position, although flatness is good, pleat can be produced in the stage of prebake conditions.As above institute State, only used with the epoxide with siloxanes key knot position as required composition it is a certain amount of in the case of, can expire The all characteristics of foot.

[industrial applicability]

The conducts such as the transparency of cured film, light resistance and resistant sputtering by obtained by the thermosetting compositionss of the present invention The characteristic of optical material is excellent, since then from the aspect of, can be used as colored filter, LED light-emitting component and light receiving element etc. Various optical materials etc. protecting film and be formed between TFT and transparency electrode and between transparency electrode and alignment films Transparent insulating film.

Claims

1. a kind of thermosetting compositionss, which is comprising polyesteramide acid, the epoxide with siloxanes key knot position, no The compositionss of the epoxide with siloxanes key knot position and epoxy curing agent, it is characterised in that：The polyesteramide acid It, by being obtained with tetracarboxylic dianhydride, diamidogen and multi-hydroxy compound as required material composition is reacted, and is logical to be Crossing makes the multi-hydroxy compound of X mole of the tetracarboxylic dianhydride, Y mole of the diamidogen and Z mole with following formula (1) and formula (2) relation set up ratio reacted and obtained polyesteramide acid,

0.2≤Z/Y≤8.0…(1)

0.2≤(Y+Z)/X≤5.0…(2)

The polyesteramide acid has construction unit and the construction unit represented by formula (4) represented by following formulas (3)；

Relative to the polyesteramide acid 100 weight portions, the epoxide with siloxanes key knot position with it is described not Epoxide with siloxanes key knot position adds up to 20 weight portion～400 weight portions；

Relative to total 100 weight portions of the epoxide, the epoxy curing agent is 0 weight portion～60 weight portion；And And,

R¹It is tetracarboxylic dianhydride's residue, R²It is diamidogen residue, R³It is multi-hydroxy compounds residues.

2. thermosetting compositionss according to claim 1, it is characterised in that：The material composition of the polyesteramide acid enters One step includes monohydric alcohol.

3. thermosetting compositionss according to claim 2, it is characterised in that：The monohydric alcohol is selected from isopropanol, alkene In propanol, benzylalcohol, hydroxyethyl methacrylate, dihydroxypropane single-ether and 3- ethyl -3- hydroxymethyl oxetanes one More than kind.

4. thermosetting compositionss according to claim 1 and 2, it is characterised in that：The raw material of polyesteramide acid into Divide.

5. thermosetting compositionss according to claim 1 and 2, it is characterised in that：The weight of the polyesteramide acid is put down Average molecular weight is 1,000～200,000.

6. thermosetting compositionss according to claim 1 and 2, it is characterised in that：The tetracarboxylic dianhydride be selected from 3, 3 ', 4,4 '-sulfobenzide. tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 2,2- [double (3,4- dicarboxyl benzene Base)] one kind in hexafluoropropane dianhydride, 1,2,3,4- butane tetracarboxylic acid dianhydrides and ethylene glycol double (dehydration trimellitate) with On.

7. thermosetting compositionss according to claim 1 and 2, it is characterised in that：The diamidogen is selected from 3,3 '-diamino One or more of base sulfobenzide. and double [4- (3- amino-benzene oxygens) phenyl] sulfones.

8. thermosetting compositionss according to claim 1 and 2, it is characterised in that：The multi-hydroxy compound is choosing From ethylene glycol, Propylene Glycol, BDO, 1,5-PD, 1,6- hexanediol, 1,7- heptandiols, 1,8- ethohexadiols and different three One or more of paracyanogen acid three (2- hydroxyethyls) ester.

9. thermosetting compositionss according to claim 1 and 2, it is characterised in that：It is described with siloxanes key knot position Epoxide be in group selected from the compound represented by the compound represented by following formula (5) and formula (6) extremely Few one kind,

R⁴、R⁵And R⁶It is separately hydrogen, hydroxyl, the organic group of carbon number 1～26 or the organic group with epoxy radicals, R⁷Respectively It independently is hydrogen, the organic group of carbon number 1～26 or the organic group with epoxy radicals, R⁴、R⁵、R⁶And R⁷At least one be have The organic group of epoxy radicals, m is more than 2 integer, R⁴Or R⁵Also can be from the R being bonded on different Si⁴Or R⁵It is bonded and forms silicon Oxygen alkane ring, also, R⁶And R⁷Can also be bonded and form siloxanes ring；

R⁸、R⁹、R¹⁰、R¹¹It is separately hydrogen or the organic group of carbon number 1～26, R¹²And R¹³Be separately hydrogen, carbon number 1～ 26 organic group or the organic group with epoxy radicals, R¹²And R¹³At least one be the organic group with epoxy radicals, n is more than 1 Integer, R⁸Or R⁹Also can be from the R being bonded on different Si⁸、R⁹、R¹⁰, or R¹¹It is bonded and forms siloxanes ring, also, R¹⁰ Or R¹¹Also can be from the R being bonded on different Si⁸、R⁹、R¹⁰, or R¹¹¹¹It is bonded and forms siloxanes ring.

10. thermosetting compositionss according to claim 1 and 2, it is characterised in that：It is described with siloxanes key knot position Epoxide be selected from by with double [2- (3, the 4- expoxycyclohexyl) ethyl] tetramethyl disiloxanes of 1,3-, 1,3- Double (3- glycidoxypropyls) tetramethyl disiloxanes, 3- glycidoxypropyltrimewasxysilanes are material composition The copolymer for being reacted and being obtained, and by with 3- glycidoxypropyltrimewasxysilanes, phenyl trimethoxy In the group that the copolymer that silane and trimethylmethoxysilane are reacted and obtained by material composition is constituted at least one Kind.

11. thermosetting compositionss according to claim 1 and 2, it is characterised in that：The epoxy curing agent is selected from inclined One or more of benzenetricarboxylic anhydride, hexahydro trimellitic anhydride and 2- undecyl imidazoles.

12. thermosetting compositionss according to claim 1, it is characterised in that：The tetracarboxylic dianhydride is 3,3 ', 4, 4 '-diphenyl ether tetracarboxylic dianhydride or 1,2,3,4- butane tetracarboxylic acid dianhydrides；

The diamidogen is 3,3 '-diamino diphenyl sulfone；

The multi-hydroxy compound is BDO；

The epoxide with siloxanes key knot position is by with 3- glycidoxypropyltrimewasxysilanes Obtained for material composition is reacted, weight average molecular weight is 1,000～200,000 copolymer；

The not epoxide with siloxanes key knot position is 2- [4- (2,3- epoxy radicals propoxyl group) phenyl] -2- [4- 1,1- double [4- ([2,3- epoxy radicals propoxyl group] phenyl) ethyl] phenyl] propane；

The epoxy curing agent is trimellitic anhydride or 2- undecyl imidazoles；Also,

A kind of 13. cured films, it is characterised in that：Which is the thermosetting group by any one of according to claim 1 to 12 Compound and obtain.

A kind of 14. colored filters, it is characterised in that：Using cured film according to claim 13 as protecting film.

A kind of 15. liquid crystal display cells, it is characterised in that：Using colored filter according to claim 14.

A kind of 16. solid-state imagers, it is characterised in that：Using colored filter according to claim 14.

A kind of 17. liquid crystal display cells, it is characterised in that：It is thin as being formed in using cured film according to claim 13 Transparent insulating film between film transistor and transparency electrode.

A kind of 18. liquid crystal display cells, it is characterised in that：Using cured film according to claim 13 as being formed in Transparent insulating film between prescribed electrode and alignment films.

A kind of 19. touch panel devices, it is characterised in that：It is transparent as being formed in using cured film according to claim 13 Transparent insulating film on electrode.

A kind of 20. LED illuminant hearts, it is characterised in that：Using cured film according to claim 13 as protection Film.