CN102640268A - Method for producing semiconductor element substrate - Google Patents

Method for producing semiconductor element substrate Download PDF

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Publication number
CN102640268A
CN102640268A CN201180004752XA CN201180004752A CN102640268A CN 102640268 A CN102640268 A CN 102640268A CN 201180004752X A CN201180004752X A CN 201180004752XA CN 201180004752 A CN201180004752 A CN 201180004752A CN 102640268 A CN102640268 A CN 102640268A
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acid
methyl
resin
group
alkene
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CN102640268B (en
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田边彰洋
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Zeon Corp
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Nippon Zeon Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/66007—Multistep manufacturing processes
    • H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
    • H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
    • H01L29/66409—Unipolar field-effect transistors
    • H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
    • H01L29/66742—Thin film unipolar transistors
    • H01L29/6675—Amorphous silicon or polysilicon transistors
    • H01L29/66765—Lateral single gate single channel transistors with inverted structure, i.e. the channel layer is formed after the gate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1248—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition or shape of the interlayer dielectric specially adapted to the circuit arrangement
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/78606—Thin film transistors, i.e. transistors with a channel being at least partly a thin film with supplementary region or layer in the thin film or in the insulated bulk substrate supporting it for controlling or increasing the safety of the device

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Thin Film Transistor (AREA)
  • Formation Of Insulating Films (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Disclosed is a method for producing a semiconductor element substrate, which involves: a step for subjecting the semiconductor element surface or the semiconductor layer element surface contained in the aforementioned semiconductor element to plasma processing; and a step for forming a passivation film formed from an organic material on the semiconductor element surface or the semiconductor element layer surface which were subjected to plasma processing.

Description

The manufacturing approach of semiconductor element substrate
Technical field
The present invention relates to a kind of manufacturing approach of semiconductor element substrate, this manufacturing approach is carried out the hydrogen plasma processing to semiconductor layer, and forms the passivating film that has used organic material.
Background technology
The semiconductor element substrate is widely used in electronic product.For example thin-film transistor is switch (switching) element that possesses the terminal that is called as gate electrode, source electrode and drain electrode, is widely used in the active element etc. of the active-matrix substrate of display elements such as active matrix (Active Matrix) type LCD or organic EL.
In existing thin-film transistor, be formed with the passivating film that constitutes by silicon nitride film (SiNx film) through sputtering method, vapour deposition method, CVD method contained semiconductor layer surface in semiconductor element or semiconductor element.In addition, from the purpose of the adaptation of the semiconductor layer that improves the SiNx film and constitute by a-Si, the surface of semiconductor layer is implemented to handle.
For example, in patent documentation 1, disclose: after semiconductor layer being carried out the hydrogen plasma processing, carry out nitrogen plasma treatment, realize improving the adaptation of semiconductor layer and passivating film and reduce the off-state leakage current.But shown in patent documentation 1, when passivating film used inorganic material, have following problem: needs carried out film forming under the state after making material generation plasmaization or ionization in a vacuum, and it is big that equipment scale becomes, trivial operations.
In addition, at this moment,, then there is the bad such problem of etching that produces, therefore, need after hydrogen plasma is handled, carries out nitrogen plasma treatment if after hydrogen plasma is handled, do not carry out nitrogen plasma treatment.And then, when passivating film uses inorganic material, when forming contact hole, need resist, therefore use the situation of organic material to compare with passivating film, it is many that operation becomes.That is, need the operation of painting erosion resistant agent to reach the operation of behind dry-etching, peeling off resist.Relative therewith, when passivating film uses organic material, need not use resist, therefore, can seek to reduce the operation number.In addition, under the situation of using inorganic material, the thickness that can be formed at the passivating film on the specific layer is restricted, and is difficult to form smooth passivating film.
In addition, in non-patent literature 1, disclose: in passivating film, use SiNx to carry out Cement Composite Treated by Plasma, can suppress initial off-state leakage current.But, under the situation of the active-matrix substrate that this semiconductor element substrate is used for display element, require high reliability.That is, require not only under the situation of initial off-state leakage current, even and under exacting terms use also can suppress the off-state leakage current and realize the raising in TFT life-span.
In addition, SiNx have stop dangling bonds function (for example the referenced patent document 2), therefore, the main purpose of the Cement Composite Treated by Plasma in patent documentation 1 and the non-patent literature 1 does not also lie in the termination dangling bonds.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2003-37269 communique
Patent documentation 2: No. the 2009/057444th, International Publication
Non-patent literature
Non-patent literature 1:Pei Ming Chen, Wan Yu Lo, Chuan Sheng Wei; Jing Jie Shih, Chih Hung Shih, Mao Song Chen; Feng Yuan Gen, and Tom Huang, " The effects of back-channel treatment on electrical characteristic of a-Si:H TFT device "; International Display Workshop ' 07, p1951-1953
Summary of the invention
The problem that invention will solve
The object of the present invention is to provide a kind of manufacturing approach of semiconductor element substrate of can fabrication reliability high semiconductor element substrate.
Solve the method for problem
The inventor etc. concentrate on studies in order to solve above-mentioned purpose; The result finds; In the manufacturing approach of semiconductor element substrate; Semiconductor layer surface contained in semiconductor component surfaces or the semiconductor element is carried out Cement Composite Treated by Plasma stop dangling bonds; In semiconductor component surfaces of having carried out Cement Composite Treated by Plasma or semiconductor component surfaces, form the passivating film that contains organic material on the contained semiconductor layer surface, even rise at the hot and humid off-state leakage current that also can suppress down, device reliability is excellent.
That is,, following content is provided according to the present invention:
(1) a kind of manufacturing approach of semiconductor element substrate, it comprises following operation:
Semiconductor layer surface contained in semiconductor component surfaces or the said semiconductor element is carried out the operation of Cement Composite Treated by Plasma; On said semiconductor component surfaces of having carried out said Cement Composite Treated by Plasma or said semiconductor layer surface, form the operation of the passivating film that contains organic material;
(2) according to the manufacturing approach of (1) described semiconductor element substrate, wherein, said Cement Composite Treated by Plasma is that hydrogen plasma is handled;
(3) according to the manufacturing approach of (1) or (2) described semiconductor element substrate, wherein, said semiconductor element or said semiconductor layer are made through following operation, and said operation comprises:
On substrate, form the operation of gate electrode, gate insulating film, semiconductor layer and source-drain electrode, and
Form the operation of channel region;
(4) according to the manufacturing approach of each described semiconductor element substrate in (1) ~ (3), wherein, said organic material is the resin combination that contains resin;
(5) according to the manufacturing approach of each described semiconductor element substrate in (1) ~ (4), wherein, the processing time of said Cement Composite Treated by Plasma is 1 ~ 10 minute.
The invention effect
According to the manufacturing approach of semiconductor element substrate of the present invention, can make the high semiconductor element substrate of a kind of reliability.
Description of drawings
Fig. 1 is the figure of operation of manufacturing approach of the semiconductor element substrate of expression execution mode of the present invention;
Fig. 2 is the figure of operation of manufacturing approach of the semiconductor element substrate of expression execution mode of the present invention;
Fig. 3 is the figure of the passivating film of expression execution mode of the present invention.
Symbol description
21 ... Substrate, 22 ... Gate electrode, 23 ... Gate insulating film, 24 ... Semiconductor layer, 25 ... Be added with the semiconductor layer, 26 of impurity ... Source-drain electrode, 27 ... Source electrode, 28 ... Drain electrode, 29 ... Channel region, 30 ... Be positioned at the semiconductor layer that is added with impurity, 31 in the existing zone of electrode, source ... Be positioned at the semiconductor layer that is added with impurity, 32 in the existing zone of drain electrode ... Contain the passivating film, 33 that organic material forms ... Contain the passivating film that organic and/or inorganic materials forms
Embodiment
Below, describe with reference to the manufacturing approach of accompanying drawing semiconductor element substrate of the present invention.Need to prove that accompanying accompanying drawing only is shape, size and the configuration that on the degree that can understand invention, roughly shows inscape, the present invention does not receive the qualification of these accompanying drawings.Therefore, omit unwanted key element when the present invention will be described, in addition, the shape of illustrated each key element, size etc. are not the reflection actual conditions yet.In addition, can be clearly in the scope of the technological thought of the present invention that does not depart from the claim to be put down in writing, can replace, be out of shape and change for the personnel of general knowledge various execution modes of the present invention with present technique field.
At first, shown in Fig. 1 (a), on insulating properties substrates 21 such as glass substrate, form gate electrode 22 through sputtering method.Then, photoresist (not shown) as mask, is carried out patterning through dry-etching or Wet-type etching that kind shown in Fig. 1 (b) to gate electrode 22.Then, shown in Fig. 1 (c) such through the CVD method deposit gate insulating film 23 successively, the semiconductor layer 24 that constitutes by amorphous silicon, the semiconductor layer 25 that is added with impurity.Then; Shown in Fig. 1 (d); With photoresist (not shown) as mask; Through dry-etching or Wet-type etching semiconductor layer 24 and the semiconductor layer 25 that is added with impurity are carried out patterning, form the semiconductor structure of the island that constitutes by semiconductor layer 24 and the semiconductor layer 25 that is added with impurity thus.
(ohm layer)
Then, shown in Fig. 2 (a), form source-drain electrode 26 through sputtering method.Then, photoresist (not shown) is as mask, such shown in Fig. 2 (b), through etching source-drain electrode 26 is carried out patterning, form source electrode 27 and drain electrode 28.That is, source electrode 27 and drain electrode 28 are that source-drain electrode 26 separates formation through patterning, and source-drain electrode 26, source electrode 27 and drain electrode 28 constitute by same material.Usually the etching of source-drain electrode is carried out through Wet-type etching, but also can be dry-etching.
Then, the not shown photoresist that directly will in the patterning of source-drain electrode 26, take place to subtract film carries out etching as mask to the semiconductor layer 25 that is added with impurity.Form channel region such shown in Fig. 2 (c).Usually the etching that is added with the semiconductor layer of impurity is carried out through dry-etching, but also can adopt Wet-type etching.At this, channel region is represented: at source electrode 27 and have the gate electrode side end of the semiconductor layer that is added with impurity 30 in the zone of active electrode and at drain electrode 28 and have the part semiconductor layer of clamping between the gate electrode side end of the semiconductor layer that is added with impurity 31 in the zone of drain electrode.That is, the part semiconductor layer of being represented by arrow of the dotted line clamping of Fig. 2 (c) is a channel region 29.
The photoresist (not shown) that uses when then, using stripper to remove patterning.Might be on substrate when removing residual organic matter residue or produce pollute etc., therefore, can after using stripper to peel off photoresist, suitably increase following operation: the matting of using the UV irradiation; Use the ashing operation of oxygen radical or their clustered operation etc., wherein, above-mentioned oxygen radical generates as follows: be main body and mixed C F with oxygen 4And N 2Deng, obtain gas, use this gas to produce plasma.
Then, channel region 29 being carried out hydrogen plasma handles and the termination dangling bonds.Hydrogen plasma is handled and was preferably carried out 1 ~ 10 minute, is carrying out can applying the bias voltage below hundreds of W, below the preferred 200W when hydrogen plasma is handled.In addition, after the Cement Composite Treated by Plasma operation, then contain when further with hydrofluoric acid above-mentioned Cement Composite Treated by Plasma face being carried out the surface-treated operation, the reliability of thin-film transistor further improves sometimes, so preferred.
Then, form the passivating film that comprises organic material.In the present invention, comprise not special qualification of passivating film of organic material, can utilize plasma CVD method or vapour deposition method, film-stack method, rubbing method etc. to carry out film forming.Wherein, because film-stack method or rubbing method can form film easy and effectively, so preferably, more preferably rubbing method.
When containing the film forming of passivating film of organic material through rubbing method, can make thin-film transistor through technology easy and that the time is short with high reliability.In addition, the preferred resin combination that contains resin and organic solvent that utilizes forms film.
Rubbing method is following method, in the operation of the oxide-film that has passed through the semiconductor layer surface of removing channel region and be formed with on the substrate of thin-film transistor behind the coating resin composition, removes and desolvates.As coating resin method for compositions on aforesaid substrate, for example can enumerate: spraying process, spin-coating method, rolling method, mould are coated with method, scraper plate method, spin-coating method, rod and are coated with method, silk screen print method etc.Through coated film being carried out drying, preferably carrying out heat drying and come to remove and to desolvate.At this moment, baking temperature can suit to select according to the kind and the compounding ingredient of each composition, is generally 30 ~ 250 ℃.Can suit to select drying time according to the kind and the cooperation ratio of each composition, but be generally 0.5 ~ 150 minute.
The film-stack method is following: resin combination is coated on B level films (B stage film) such as resin molding or metal film and forms with on the substrate; Obtain B level film (B stage film) except that desolvating; Then, this B level film (B stage film) is layered on the aforesaid substrate.Carry out drying, preferably carry out heat drying and remove and desolvate through the B level film (B stage film) after the coating being formed with substrate.At this moment, drying condition can suit to select according to the kind and the cooperation ratio of each composition, and baking temperature is generally 30 ~ 150 ℃, is generally 0.5 ~ 90 minute drying time.Can use press-connection machines such as pressure level press, pressing machine, vacuum laminator, vacuum pressing-combining machine, roll-type laminating machine to carry out film-stack.
As stated, form the passivating film that contains organic material being formed with on the substrate of thin-film transistor.The thickness of passivating film is generally 0.1 ~ 100 μ m, is preferably 0.5 ~ 50 μ m, and more preferably 0.5 ~ 30 μ m most preferably is 0.5 ~ 10 μ m.Thickness through making passivating film can be manufactured on the thin-film transistor that also has high reliability under the harsh atmosphere easily in above-mentioned scope.The thickness of passivating film is crossed when thin, and protective value descends and causes the reliability variation, or because the particle when making etc. are former thereby rate of finished products is reduced, defect rate increases.When the thickness of passivating film was blocked up, because the stress of passivating film increases, protective value descended and causes the reliability variation.
In addition, comprising at passivating film under the situation of inorganic material, is 200 ~ 400nm with film thickness monitoring.Therefore, compare with the passivating film that comprises inorganic material 33 shown in Fig. 3 (b), such passivating film 32 that contains organic material can be realized planarization shown in Fig. 3 (a).
The employed passivating film that contains organic material preferably utilizes the resin combination that contains resin (A) and organic solvent (B) to form among the present invention.
In the present invention; Resin (A) is not special to be limited, and for example can enumerate: cyclic olefin resin, acrylic resin, acrylamide resin, polysiloxanes, epoxy resin, phenolic resins, Cardo resin, polyimides, polyamidoimide, Merlon, PETG, contain the resin of the monomeric unit shown in the formula (1) etc.Wherein, preferably comprise at least a resin that is selected from cyclic olefin resin, acrylic resin, Cardo resin, polysiloxanes and the polyimide resin.Wherein, consider that more preferably cyclic olefin resin as cyclic olefin resin, especially preferably has the cyclic olefin resin of protic polar group and contains the resin of the unit (e) of the monomer shown in the general formula (1) from the viewpoint of the reliability of thin-film transistor.
[Chemical formula 1]
Figure BDA00001707784100061
(in the above-mentioned formula (1), R 1The branched-chain alkyl of expression carbon number 5 ~ 16.)
These resins can distinguish independent use or combination is used two or more.
The protic polar group is meant and contains the group that Direct Bonding has the atom that belongs to the periodic table of elements the 15th family or the 16th family of hydrogen atom.The atom that belongs to the periodic table of elements the 15th family or the 16th family preferably belongs to the atom in the 1st or the 2nd cycle of the periodic table of elements the 15th family or the 16th family, and more preferably oxygen atom, nitrogen-atoms or sulphur atom are preferably oxygen atom especially.
As the concrete example of protic polar group, can enumerate: hydroxyl, carboxyl (hydroxycarbonyl group), sulfonic group, phosphate etc. have the polar group of oxygen atom; Primary amine groups, secondary amine, primary amide base, secondary amide base (imide) etc. have the polar group of nitrogen-atoms; Mercaptos etc. have the polar group of sulphur atom etc.Wherein, preferably has the group of oxygen atom, more preferably carboxyl.
In the present invention, be bonded to not special qualification of protic polar group quantity on the cyclic olefin resin with protic polar group, in addition, can contain different types of protic polar group.
In the present invention, cyclic olefin resin is homopolymers or the copolymer with cyclic olefin monomers of alicyclic structure and carbon-to-carbon double bond.Cyclic olefin resin also can have the unit by the monomer derived outside the cyclic olefin monomers.
In the entire infrastructure unit of cyclic olefin resin, the ratio of cyclic olefin monomers unit is generally 30 ~ 100 weight %, is preferably 50 ~ 100 weight %, more preferably 70 ~ 100 weight %.
In the cyclic olefin resin with protic polar group, the protic polar group can be bonded to the cyclic olefin monomers unit, also can be bonded to the monomeric unit outside the cyclic olefin monomers, but preferably is bonded to the cyclic olefin monomers unit.
As the monomer that is used to constitute cyclic olefin resin with protic polar group; Can enumerate: have the cyclic olefin monomers (a) of protic polar group, cyclic olefin monomers (b), the cyclic olefin monomers (c) that does not have polar group and the monomer (d) outside the cyclic olefin (below, abbreviate these monomers as monomer (a) ~ (d)) with the polar group outside the protic polar group.Here, monomer (d) can have the polar group beyond protic polar group or the protic polar group, also can not have polar group fully.
In the present invention, the cyclic olefin resin with protic polar group further preferably is made up of monomer (a) and monomer (b) preferably by monomer (a) and monomer (b) and/or monomer (c) formation.
Concrete example as monomer (a); Can enumerate: 5-hydroxycarbonyl group dicyclo [2.2.1] hept-2-ene", 5-methyl-5-hydroxycarbonyl group dicyclo [2.2.1] hept-2-ene", 5-carboxyl methyl-5-hydroxycarbonyl group dicyclo [2.2.1] hept-2-ene", 5,6-dihydroxy carbonyl dicyclo [2.2.1] hept-2-ene", 9-hydroxycarbonyl group Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-methyl-9-hydroxycarbonyl group Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9,10-dihydroxy carbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-carboxylic cyclic olefins such as 4-alkene; 5-(4-hydroxy phenyl) dicyclo [2.2.1] hept-2-ene", 5-methyl-5-(4-hydroxy phenyl) dicyclo [2.2.1] hept-2-ene", 9-(4-hydroxy phenyl) Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-methyl-9-(4-hydroxy phenyl) Fourth Ring [6.2.1.1 3,6.0 2,7] cyclic olefin etc. of 12 carbon-hydroxyls such as 4-alkene, wherein, preferred carboxylic cyclic olefin.These cyclic olefin monomers (a) with protic polar group can be distinguished independent use, also can make up use two or more.
The concrete example of the polar group outside the protic polar group that is had as the cyclic olefin monomers with the polar group outside the protic polar group (b) can be enumerated: ester group (general name of alkoxy carbonyl and aryloxycarbonyl), N-substituted imides base, epoxy radicals, halogen atom, cyanic acid, ketonic oxygen base carbonyl (the acid anhydrides residue of dicarboxylic acids), alkoxyl, carbonyl, tertiary amine groups, sulfo group, acryloyl group etc.Wherein, preferred ester group, N-substituted imides base and cyanic acid, more preferably ester group and N-substituted imides base, especially preferably N-substituted imides base.As the concrete example of monomer (b), can enumerate following cyclic olefin.
As cyclic olefin, for example can enumerate: 5-acetoxyl group dicyclo [2.2.1] hept-2-ene", 5-methoxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-methyl-5-methoxycarbonyl dicyclo [2.2.1] hept-2-ene", 9-acetoxyl group Fourth Ring [6.2.1.1 with ester group 3,6.0 2,7] 12 carbon-4-alkene, 9-methoxycarbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-ethoxy carbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-positive propoxy carbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-isopropoxy carbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-n-butoxy carbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-methyl-9-methoxycarbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-methyl-9-ethoxy carbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-methyl-9-positive propoxy carbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-methyl-9-isopropoxy carbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-methyl-9-n-butoxy carbonyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-(2,2,2-trifluoro ethoxy carbonyl) Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-methyl-9-(2,2,2-trifluoro ethoxy carbonyl) Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene etc.
As cyclic olefin with N-substituted imides base; For example can enumerate: N-phenyl dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(2-ethylhexyl)-1-isopropyl-4-methyl bicycle [2.2.2] suffering-5-alkene-2; 3-dicarboxyl acid imide, N-(2-ethylhexyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-[(2-ethyl butoxy) ethoxycarbonyl propyl]-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide etc.
As cyclic olefin, for example can enumerate: 9-cyanic acid Fourth Ring [6.2.1.1 with cyanic acid 3,6.0 2,7] 12 carbon-4-alkene, 9-methyl-9-cyanic acid Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 5-cyano-bicyclo [2.2.1] hept-2-ene" etc.
As cyclic olefin, for example can enumerate: 9-chlorine Fourth Ring [6.2.1.1 with halogen atom 3,6.0 2,7] 12 carbon-4-alkene, 9-methyl-9-chlorine Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene etc.
These cyclic olefin monomers (b) with the polar group beyond the protic polar group can distinguish independent use also can make up use two or more.
As the concrete example of the cyclic olefin monomers (c) that does not have polar group fully, can enumerate: dicyclo [2.2.1] hept-2-ene" (being also referred to as " ENB "), 5-ethyl-dicyclo [2.2.1] hept-2-ene", 5-butyl-dicyclo [2.2.1] hept-2-ene", 5-ethylidene-dicyclo [2.2.1] hept-2-ene", 5-methylene-dicyclo [2.2.1] hept-2-ene", 5-vinyl-dicyclo [2.2.1] hept-2-ene", three ring [5.2.1.0 2,6] last of the ten Heavenly stems-3, dicyclopentadiene), Fourth Ring [10.2.1.0 8-diene (common name: 2,11.0 4,9] 15 carbon-4,6,8,13-tetraene, Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene (is also referred to as " tetracyclododecen ".), 9-methyl-Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-ethyl-Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-methylene-Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-ethylidene-Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-vinyl-Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, 9-acrylic-Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, five rings [9.2.1.1 3,9.0 2,10] 15 carbon-5,12-diene, cyclopentene, cyclopentadiene, 9-phenyl-Fourth Ring [6.2.1.1 3,6.0 2,7] 12 carbon-4-alkene, Fourth Ring [9.2.1.0 2,10.0 3,8] 14 carbon-3,5,7,12-tetraene, five rings [9.2.1.1 3,9.0 2,10] 15 carbon-12-alkene etc.These cyclic olefin monomers (c) that do not have polar group fully can be distinguished independent use, also can make up use two or more.
As the concrete example of the monomer (d) beyond the cyclic olefin, can enumerate chain alkene.As chain alkene; For example can enumerate: ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 3-methyl-1-butene, 3-Methyl-1-pentene, 3-ethyl-1-amylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 4; 4-dimethyl-1-hexene, 4, the alpha-olefin of carbon numbers 2 ~ 20 such as 4-dimethyl-1-amylene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-laurylene, 1-tetradecylene, 1-hexadecylene, 1-octadecylene, 1-icosa alkene; 1,4-hexadiene, 4-methyl isophthalic acid, 4-hexadiene, 5-methyl isophthalic acid, 4-hexadiene, 1, non-conjugated dienes such as 7-octadiene etc.Monomer (d) beyond these cyclic olefins can distinguish independent use or also can make up use two or more.
Being used for the cyclic olefin resin with protic polar group of the present invention can be through obtaining monomer (a) with the monomer polymerization that is selected from monomer (b) ~ (d) according to expectation.The polymer that can further obtain polymerization carries out hydrogenation.Be also contained in through the polymer of hydrogenation and be used for the cyclic olefin resin with protic polar group of the present invention.
In addition; The cyclic olefin resin with protic polar group that uses among the present invention also can obtain through following method: utilize known modifier in the cyclic olefin resin that does not have the protic polar group, to import the protic polar group, carry out hydrogenation according to expectation.Polymer before also can importing the protic polar group carries out hydrogenation.In addition, also can carry out further modification and import the protic polar group cyclic olefin resin with protic polar group.Can and make capable polymerization do not had the polymer of protic polar group through the above-mentioned monomer of combination in any (b) ~ (d).
As the modifier that is used to import the protic polar group, can use the compound that in a molecule, has protic polar group and reactive carbon-to-carbon unsaturated bond usually.As the concrete example of such compound, can enumerate: unsaturated carboxylic acids such as acrylic acid, methacrylic acid, angelic acid, tiglic acid, oleic acid, elaidic acid, erucic acid, brassidic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, atropic acid, cinnamic acid; Unsaturated alcohols such as allyl alcohol, methyl ethylene methyl alcohol, crotonyl alcohol, methylallyl alcohol, 1-styrene-1-alcohol, 2-amylene-1-ol, 3-butene-1-alcohol, 3-butene-2-alcohol, 3-methyl-3-butene-1-alcohol, 3-methyl-2-butene-1-alcohol, 2-methyl-3-butene-2-alcohol, 2-methyl-3-butene-1-alcohol, 4-amylene-1-ol, 4-methyl-4-amylene-1-ol, 2-hexen-1-ol etc.Use the cyclic olefin resin modified-reaction of this modifier to adopt common method to get final product, for example can in the presence of free-radical generating agent, carry out.
Be used for adopting common method to get final product with the polymerization that the monomer that is selected from monomer (b) ~ (d) according to expectation carries out polymerization monomer (a), for example can adopt ring-opening polymerisation method or addition polymerization method.
As polymerization catalyst, for example can preferably use metal complexs such as molybdenum, ruthenium, osmium.These polymerization catalysts can distinguish independent use or also can make up use two or more.The amount of polymerization catalyst is with the metallic compound in the polymerization catalyst: the molar ratio computing of cyclic olefin is usually at 1: 100 ~ 1: 2,000,000 scope, and preferably at 1: 500 ~ 1: 1,000,000 scope, more preferably at 1: 1,000 ~ 1: 500,000 scope.
Each monomer of polymerization and the hydrogenation of the polymer that obtains uses hydrogenation catalyst to carry out usually.As hydrogenation catalyst, for example can use common employed catalyst when olefin(e) compound hydrogenation.Particularly, can utilize homogeneous catalyst, noble metal complexes catalyst and the solid supported noble metal series catalysts etc. of Ziegler-type.
In these hydrogenation catalysts, never can cause that side reaction such as functional group modification and the aspect that can be optionally carry out hydrogenation to the carbon-to-carbon unsaturated bond of the main chain in the polymer consider noble metal complexes catalyst such as preferred rhodium, ruthenium.Preferred especially coordination has to the high nitrogen heterocyclic ring formula carbene compound of electronics property or the ruthenium catalyst of phosphine class.
Hydrogenation ratio through the main chain of the polymer of hydrogenation is generally more than 90%, is preferably more than 95%, more preferably more than 98%.Hydrogenation ratio is when this scope, and the thermal endurance of resin (A) is excellent especially, so preferred.Can pass through 1H-NMR spectrum is measured the hydrogenation ratio of resin (A).For example: can obtain with the form of the ratio of the carbon-to-carbon double bond molal quantity before the carbon-to-carbon double bond molal quantity of hydrogenation is with respect to hydrogenation.
In the present invention, preferred as cyclic olefin resin particularly like the resin shown in following with the construction unit shown in the formula (2) with protic polar group, more preferably have the resin of the construction unit shown in construction unit shown in the formula (2) and the formula (3).
[Chemical formula 2]
Figure BDA00001707784100101
[in the formula (2), R 1~ R 4Respectively be independently hydrogen atom or-X n(X is the organic group of divalence to-R ' base; N is 0 or 1; R ' is for having substituent alkyl, can having substituent aromatic group or protic polar group).R 1~ R 4In at least one when R ' be protic polar group time-X n-R ' base.M is 0 ~ 2 integer.]
[chemical formula 3]
Figure BDA00001707784100111
[in the formula (3), R 5~ R 8Follow two carbon atoms that are bonded together with them as the oxygen atom that becomes annular atoms formation to contain or 3 ~ 5 yuan of heterocycle structures of nitrogen-atoms to make up arbitrarily, this heterocycle can have substituting group on this heterocycle.K is 0 ~ 2 integer.]
In the general formula (2),, can enumerate methylene, ethylidene and carbonyl etc. as the example of the organic group of the represented divalence of X.
Can have the alkyl that substituent alkyl is generally the carbon number 1 ~ 7 of straight or branched shown in the R ',, can enumerate methyl, ethyl, n-pro-pyl, isopropyl etc. as its example.Can have substituent aromatic group and be generally the aromatic group of carbon number 6 ~ 10, as its example, can enumerate: phenyl, benzyl etc.As the substituent example of these alkyl or aromatic group, can enumerate: the alkyl of carbon numbers 1 ~ 4 such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group; The aryl of carbon numbers such as phenyl, xylyl, tolyl, naphthyl 6 ~ 12 etc.
As the protic polar group shown in the R ', can enumerate aforesaid group.In the general formula (3), as R 5~ R 8With 3 yuan of heterocycle structures that combination arbitrarily follows two carbon atoms being bonded together with them to form, can enumerate epoxy construction etc.In addition, same, as the example of 5 yuan of heterocycle structures, can enumerate: the dicarboxylic anhydride structure [C (=O)-O-C (=O)-], the dicarboxyl imide structure [C (=O)-N-C (=O)-] etc.As the substituent example that is bonded to this heterocycle, can enumerate phenyl, naphthyl, anthryl etc.
The acrylic resin that uses among the present invention is not special to be limited, preferably to be selected from carboxylic acid with acrylic, to have the carboxylic acid anhydrides of acrylic or contain at least a homopolymers or the copolymer as monomer in the epoxy acrylate compound.
As the concrete example of carboxylic acid, can enumerate: (methyl) acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconate etc. with acryloyl group; As the concrete example of carboxylic acid anhydrides, can enumerate: maleic anhydride, citraconic anhydride etc. with acrylic; As the concrete example that contains the epoxy acrylate compound; Can enumerate: glycidyl acrylate, GMA, α-Yi Jibingxisuan ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, acrylic acid-3; 4-epoxy butyl ester, methacrylic acid-3,4-epoxy butyl ester, acrylic acid-6,7-epoxy heptyl ester, methacrylic acid-6; 7-epoxy heptyl ester, α-Yi Jibingxisuan-6,7-epoxy heptyl ester etc.
Wherein, preferred (methyl) acrylic acid, maleic anhydride, GMA, methacrylic acid-6,7-epoxy heptyl ester etc.In the present invention, " (methyl) acrylic acid " is meant any one in methacrylic acid and the acrylic acid.
But acrylic resin can be for being selected from unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides and containing the copolymer that the monomer of at least a monomer and the copolymerization beyond other acrylic ester monomer or the acrylic acid ester in the unsaturated compound of epoxy radicals forms.As other acrylic ester monomer, can enumerate: (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) tert-butyl acrylate, (methyl) EHA, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) lauryl acrylate, (methyl) acrylic acid stearyl; (methyl) acrylic acid hydroxyalkyl acrylates such as (methyl) Hydroxyethyl Acrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester; (methyl) acrylic acid phenoxy ethyl, (methyl) acrylic acid 2-hydroxyl-(methyl) acrylic acid phenoxyalkyl esters such as 3-phenoxy group propyl ester; (methyl) alkoxyalkyl acrylates such as (methyl) acrylic acid 2-methoxyl group ethyl ester, (methyl) acrylic acid 2-ethoxy ethyl ester; PAG (methyl) acrylic acid ester such as polyethyleneglycol (methyl) acrylic acid ester, ethyoxyl diethylene glycol (methyl) acrylic acid ester, methoxy poly (ethylene glycol) (methyl) acrylic acid ester, phenoxy group polyethylene glycol (methyl) acrylic acid ester; (methyl) acrylic acid cycloalkyl esters such as (methyl) cyclohexyl acrylate, (methyl) acrylic acid 4-butyl cyclohexyl, (methyl) acrylic acid two cyclopentyl esters, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid bicyclopentadiene ester, (methyl) acrylic acid norbornene ester, (methyl) IBOA, (methyl) acrylic acid three ring esters in the last of the ten Heavenly stems; (methyl) benzyl acrylate, (methyl) tetrahydrofurfuryl acrylate etc.Wherein, preferred (methyl) butyl acrylate, (methyl) EHA, (methyl) lauryl acrylate, (methyl) isodecyl acrylate and (methyl) acrylic acid 2-ethoxy ethyl ester etc.
As the copolymerisable monomer beyond the acrylic acid ester; If can be with above-mentioned carboxylic acid with acrylic, have the carboxylic acid anhydrides of acrylic or contain the just not special restriction of compound of epoxy acrylate compound copolymerization, for example can enumerate: vinyl benzyl methyl ether, vinyl glycidyl ether, styrene, AMS, butadiene, isoprene etc. contain the vinyl free-radical polymerised compound.These compounds can be distinguished independent use, also can make up use two or more.The polymerization of above-mentioned monomer adopts common method to get final product, and for example can adopt suspension polymerization, emulsion polymerization, solution polymerization process etc.
The Cardo resin is meant to have the Cardo structure, that is, two circuluses are bonded to the resin of the skeleton structure that forms on the quaternary carbon atom that constitutes circulus.The common structure of Cardo structure is that phenyl ring is bonded to the structure that the fluorenes ring forms.
Be bonded to the concrete example of the skeleton structure that forms on the quaternary carbon atom that constitutes circulus as two circuluses, can enumerate: fluorene skeleton, bisphenol fluorene skeleton, two aminophenyl fluorene skeleton, have epoxy radicals fluorene skeleton, have the fluorene skeleton of acryloyl group etc.
With regard to the Cardo resin that uses among the present invention, the skeleton with this Cardo structure can carry out polymerization through reaction between the bonding functional group on it etc. and form.The Cardo resin has the structure (Cardo structure) that forms with an element connection main chain and bulky side chain, has circulus in the direction with respect to the main chain approximate vertical.
Cardo example of structure with epoxy glycidol ether structure is shown in formula (4).
[chemical formula 4]
Figure BDA00001707784100131
(in the formula (4), n representes 0 ~ 10 integer.)
As monomer, for example can enumerate: two (glycidoxypropyl phenyl) fluorenes type epoxy resin with Cardo structure; The condensation product that bisphenol fluorene type epoxy resin and acrylic acid form; 9, two (4-hydroxy phenyl) fluorenes, 9 of 9-, two (the 4-hydroxy-3-methyl phenyl) fluorenes etc. of 9-contain the bisphenols of Cardo structure; 9, two (cyano methyl) fluorenes of 9-etc. 9, two (cyanic acid alkyl) the fluorenes classes of 9-; 9, two (3-aminopropyl) fluorenes of 9-etc. 9, two (aminoalkyl) fluorenes classes of 9-etc.The polymer that the Cardo resin obtains for the monomer polymerization that will have the Cardo structure, but the copolymer that also can form for the monomer of copolymerization with other.The polymerization of above-mentioned monomer adopts common method to get final product.
The structure of the polysiloxanes that uses among the present invention is not special to be limited, and can preferably enumerate more than one and polysiloxanes that its reaction is obtained through the organosilan shown in hybrid (5).
[chemical formula 5]
Figure BDA00001707784100141
R in the formula (5) 9In the aryl of the alkyl of expression hydrogen, carbon number 1 ~ 10, the alkenyl of carbon number 2 ~ 10, carbon number 6 ~ 15 any one, a plurality of R 9Can be the same or different respectively.In addition, these alkyl, alkenyl and aryl all can have substituting group, in addition, also can be not have substituent nothing to replace body, can select according to the characteristic of composition.Concrete example as alkyl; Can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, positive decyl, trifluoromethyl, 2; 2,2-trifluoroethyl, 3,3; 3-trifluoro propyl, 3-glycidoxy propyl group, 2-(3, the 4-epoxycyclohexyl) ethyl, 3-aminopropyl, 3-sulfydryl propyl group, 3-NCO propyl group.As the concrete example of alkenyl, can enumerate: vinyl, 3-acryloxy propyl group, 3-methacryloxypropyl.As the concrete example of aryl, can enumerate: phenyl, tolyl, p-hydroxybenzene, 1-(p-hydroxybenzene) ethyl, 2-(p-hydroxybenzene) ethyl, 4-hydroxyl-5-(p-hydroxybenzene ketonic oxygen base) amyl group, naphthyl.
R in the formula (5) 10In the aryl of the alkyl of expression hydrogen, carbon number 1 ~ 6, the acyl group of carbon number 1 ~ 6, carbon number 6 ~ 15 any one, a plurality of R 10Can be the same or different respectively.In addition, these alkyl, acyl group all can have substituting group, also can replace body for not having substituent nothing in addition, can select according to the characteristic of composition.As the concrete example of alkyl, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl.As the concrete example of acyl group, can enumerate: acetyl group.As the concrete example of aryl, can enumerate: phenyl.N in the formula (5) representes 0 ~ 3 integer.N be 0 o'clock be 4 functional silanes, n be 1 o'clock be 3 functional silanes, n be 2 o'clock be 2 functional silanes, at n be 3 o'clock be 1 functional silanes.
As the concrete example of the organosilan shown in the formula (5), can enumerate: 4 functional silanes such as tetramethoxy-silicane, tetraethoxysilane; 3 functional silanes such as MTMS, MTES, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl three isopropoxy silane, ethyl three n-butoxy silane, n-pro-pyl trimethoxy silane, normal-butyl trimethoxy silane, n-hexyl trimethoxy silane, n-hexyl triethoxysilane, decyl trimethoxy silane, vinyltrimethoxy silane, VTES, 3-methacryloxypropyl trimethoxy silane, 3-acryloxy propyl trimethoxy silicane, phenyltrimethoxysila,e, p-hydroxybenzene trimethoxy silane, 2-(p-hydroxybenzene) ethyl trimethoxy silane, 4-hydroxyl-5-(p-hydroxybenzene carbonyl oxygen base) amyltrimethoxysilane, trifluoromethyl trimethoxy silane, 3-TSL 8330,3-aminopropyltriethoxywerene werene, 3-glycidoxypropyltrime,hoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane; 2 functional silanes such as dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl diacetoxy silane, di-n-butyl dimethoxy silane, dimethoxydiphenylsilane; 1 functional silanes such as trimethyl methoxy silane, three normal-butyl Ethoxysilanes.
In these organosilans, consider, can preferably use 3 functional silanes from the resistance to cracking of the resin molding that obtains by resin combination of the present invention and the aspect of hardness.In addition, these organosilans can use separately also can make up use two or more.
Polysiloxanes among the present invention can be through being hydrolyzed above-mentioned organosilan and the part condensation obtains.Hydrolysis and part condensation can be used usual way.For example in mixture, add solvent, water and catalyst as required and carry out heated and stirred.In the stirring, can come dephlegmate to separate accessory substance alcohol such as () methyl alcohol or condensation by-product (water) through distillation according to necessity.
The polyimides that uses among the present invention can obtain through the polyimide precursor that tetracarboxylic anhydride and diamines is reacted obtain is heat-treated.As the precursor that is used to obtain polyimide resin, have polyamic acid, poly amic acid ester, gather different acid imide, polyamic acid sulfonamide etc.
As can particularly, enumerating: pyromellitic acid dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2 as the acid dianhydride of polyimides raw material; 3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 3; 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 2; Two (3,4-dicarboxyl phenyl) the propane dianhydrides, 2 of 2-, two (2,3-dicarboxyl phenyl) the propane dianhydrides, 1 of 2-, two (3,4-dicarboxyl phenyl) the ethane dianhydrides, 1 of 1-; Two (2,3-dicarboxyl phenyl) the ethane dianhydrides of 1-, two (3,4-dicarboxyl phenyl) methane dianhydride, two (2,3-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, 1; 2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 2; 3,5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2; Aromatic tetracarboxylic acid's dianhydride and butane tetracarboxylic acid dianhydrides, 1,2,3 such as two (3, the 4-dicarboxyl phenyl) hexafluoropropane dianhydrides of 2-, aliphat tetracarboxylic dianhydrides such as 4-pentamethylene tetracarboxylic dianhydride etc.These acid dianhydrides can use or make up two or more uses separately.
As the concrete example that can be used as the diamines of polyimides raw material, can enumerate: 3,4 '-diamino-diphenyl ether, 4,4 '-diamino-diphenyl ether, 3; 4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, 3,4 '-diamino diphenyl sulfone, 4,4 '-diamino diphenyl sulfone, 3; 4 '-diaminodiphenyl sulfide, 4,4 '-diaminodiphenyl sulfide, 1, two (4-amino-benzene oxygen) benzene of 4-, volatile oil (ベ Application ジ Application), m-phenylene diamine (MPD), p-phenylenediamine (PPD), 1,5-naphthylenediamine, 2; 6-naphthylenediamine, two (4-amino-benzene oxygen phenyl) sulfone, two (3-amino-benzene oxygen phenyl) sulfone, two (4-amino-benzene oxygen) biphenyl, two { 4-(4-amino-benzene oxygen) phenyl } ether, 1, two (4-amino-benzene oxygen) benzene, 2 of 4-, 2 '-dimethyl-4,4 '-benzidine, 2; 2 '-diethyl-4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3; 3 '-diethyl-4,4 '-benzidine, 2,2 '; 3,3 '-tetramethyl-4,4 '-benzidine, 3; 3 ', 4,4 '-tetramethyl-4; 4 '-benzidine, 2,2 '-two (trifluoromethyl)-4, or are replaced in compound that these aromatic rings form and aliphat cyclohexanediamine, di-2-ethylhexylphosphine oxide cyclohexylamine etc. with alkyl or halogen atom at 4 '-benzidine.These diamines can use or make up two or more uses separately.
The polyimides that uses among the present invention can synthesize through known method.Promptly; Can synthesize through following known method: optionally make up tetracarboxylic dianhydride and diamines and make them at N-N-methyl-2-2-pyrrolidone N-, N; N-dimethylacetylamide, N react in dinethylformamide, dimethyl sulfoxide (DMSO), HMPA, gamma-butyrolacton, the cyclopentanone isopolarity solvent etc.
The resin that contains the monomeric unit (e) shown in the general formula (1) that uses among the present invention is to contain through the monomer shown in the formula (1) being carried out the cyclic olefin resin that unit (e) that polymerization obtains forms.
[chemical formula 6]
(in the above-mentioned formula (1), R 1The branched-chain alkyl of expression carbon number 5 ~ 16.)
In the above-mentioned general formula (1), R 1Be the branched-chain alkyl of carbon number 5 ~ 16, for example can enumerate: 1-methyl butyl, 2-methyl butyl, 1-methyl amyl, 1-ethyl-butyl, 2-methyl hexyl, 2-ethylhexyl, 4-methylheptyl, 1-methyl nonyl, 1-methyl tridecyl, 1-methyl myristyl etc.Wherein, because thermal endurance and the dissolubility in organic solvent are more excellent, so the branched-chain alkyl of preferred carbon number 6 ~ 14, the more preferably branched-chain alkyl of carbon number 7 ~ 10.Carbon number is 4 when following, poorly soluble in organic solvent, and carbon number is 17 when above, the thermal endurance variation, and then, thereby there is patterned resin molding because heat and problem that fusion causes pattern to disappear.
As the concrete example of the monomer shown in the above-mentioned general formula (1), can enumerate: N-(1-methyl butyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-methyl butyl)-dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(1-methyl amyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-methyl amyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-ethyl-butyl)-dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(2-ethyl-butyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-methyl hexyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-methyl hexyl)-dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(3-methyl hexyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-butyl amyl group)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-butyl amyl group)-dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(1-methylheptyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-methylheptyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(3-methylheptyl)-dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(4-methylheptyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-ethylhexyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-ethylhexyl)-dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(3-ethylhexyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-propyl group amyl group)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-propyl group amyl group)-dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(1-methylheptyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-methylheptyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(3-methylheptyl)-dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(4-methylheptyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-ethyl heptyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-ethyl heptyl)-dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(3-ethyl heptyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(4-ethyl heptyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-propyl group hexyl)-dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(2-propyl group hexyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(3-propyl group hexyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-methyl nonyl)-dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(2-methyl nonyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(3-methyl nonyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(4-methyl nonyl)-dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(5-methyl nonyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-ethyl octyl group)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-ethyl octyl group)-dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(3-ethyl octyl group)-dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(4-ethyl octyl group)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-methyl decyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-methyl dodecyl)-dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(1-methyl undecyl)-dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(1-methyl dodecyl)-dicyclo [2.2.1] heptan-5-alkene 2,3-dicarboxyl acid imide, N-(1-methyl tridecyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(1-methyl myristyl)-dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboxyl acid imide, N-(1-methyl pentadecyl)-dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide etc.In addition, these can use separately respectively, also can make up use two or more.
As the manufacturing approach of the monomer shown in the above-mentioned general formula (1), not special the qualification for example can be through corresponding amine and 5-ENB-2, the amidation process of 3-dicarboxylic anhydride and obtaining.In addition, can through with known method to the reactant liquor of amidation process separate, purifying system separates efficiently the monomer that obtains.
Containing of monomeric unit (e) shown in the above-mentioned general formula (1) in the resin (A) proportionally is preferably 10 ~ 90 moles of % with respect to the monomeric unit total amount.Containing of monomeric unit (e) shown in the above-mentioned general formula (1) is proportional when very few, might the dissolubility of resin (A) in organic solvent become insufficient, and in the time of too much, radiation-sensitive that might resin combination reduces, or it is residual when developing, to produce dissolving.
In addition, the monomeric unit (e) shown in the above-mentioned general formula (1) contains proportional more preferably scope according to the kind of the passivating film that is made up of the resin combination that uses among the present invention and difference.Particularly; When this passivating film is to be formed by the resin combination that contains the radioactive ray sensitive compound; Utilize photoetching process to carry out under the situation of passivating film of patterning, the monomeric unit (e) shown in the above-mentioned general formula (1) contain proportional 30 ~ 60 moles of % more preferably, be preferably 40 ~ 50 moles of % especially.On the other hand, do not carry out proportional 20 ~ 80 moles of % more preferably that contain of the monomeric unit (e) shown in the above-mentioned general formula (1) under the situation of passivating film of patterning for utilizing photoetching process, be preferably 30 ~ 70 moles of % especially at passivating film.
Preferred above-mentioned general formula (1) but shown in the copolymer that forms through copolymerization of the unit of monomer of monomer and copolymerization.But, can enumerate: above-mentioned cyclic olefin monomers (a) with protic polar group, have the monomer (d) beyond cyclic olefin monomers (b), the cyclic olefin monomers (c) that does not have polar group and the cyclic olefin of the polar group beyond the protic polar group except that the monomer shown in the general formula (1) as the monomer of copolymerization.
In addition, also can be make above-mentioned general formula (1) but shown in monomer in at least aly carry out the ring-opening polymerization polymer that ring-opening polymerisation forms with the monomer of employed copolymerization as required.
As polymerization catalyst, can preferably use the metal complex of above-mentioned for example molybdenum, ruthenium, osmium etc.These polymerization catalysts can use separately respectively maybe can make up use two or more.
In addition, use hydrogenation catalyst that the polymer that each monomer polymerization forms is carried out hydrogenation.As hydrogenation catalyst, can use as stated for example common employed material when the hydrogenation of olefin(e) compound.Particularly, can utilize Ziegler-type homogeneous catalyst, noble metal complexes catalyst and solid supported noble metal series catalysts etc.In these hydrogenation catalysts; Never can cause side reactions such as functional group modification; And can optionally carry out the aspect consideration of hydrogenation to the carbon-to-carbon unsaturated bond of the main chain in the polymer; Noble metal complexes catalyst such as preferred rhodium, ruthenium, preferred especially coordination have to the high nitrogen heterocyclic ring formula carbene compound of electronics property or the ruthenium catalyst of phosphine class.
The weight average molecular weight (Mw) of employed resin (A) is usually 1,000 ~ 1 among the present invention, 000,000 scope, and preferably 1,500 ~ 100,000 scope, more preferably 2,000 ~ 10,000 scope.
The molecular weight distribution of resin (A), is preferably below 3 than being generally below 4 in weight-average molecular weight/number-average molecular weight (Mw/Mn), more preferably below 2.5.
The weight average molecular weight (Mw) and the molecular weight distribution of resin (A) can use gel permeation chromatography to measure.For example can adopt the oxolane equal solvent as elutriant, try to achieve as the polystyrene conversion molecular weight.
Employed organic solvent (B) is not special among the present invention limits.As its concrete example, can enumerate: aklylene glycol classes such as ethylene glycol, propane diols, diethylene glycol, triethylene glycol, TEG; Alkylene glycol mono ethers such as ethylene glycol monoethyl ether, dihydroxypropane single-ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether; Aklylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl-methyl ether, DPG dimethyl ether, DPG diethyl ether, DPG B ether; Alkylene glycol monoalkyl ethers ester classes such as propylene glycol methyl ether acetate, dipropylene glycol monomethyl ether acetic acid esters, propylene glycol monoethyl ether acetate; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2 pentanone, cyclohexanone, cyclopentanone; Methyl alcohol, ethanol, propyl alcohol, butanols, 3-methoxyl group-alcohols such as 3-methyl butanol; Ring-type such as oxolane, diox ethers; Cellosolve such as methylcellosolve acetate, ethyl cellosolve acetate ester class; Benzene,toluene,xylenes etc. are aromatic hydrocarbon based; Ester classes such as ethyl acetate, butyl acetate, ethyl lactate, 2-hydroxy-2-methyl methyl propionate, 3-ethoxyl ethyl propionate, 3-ethoxy-propionic acid methyl esters, gamma-butyrolacton; N-NMF, N, dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, N-methylacetamide, N, amide-types such as N-dimethylacetylamide; Sulfone classes such as dimethyl sulfoxide (DMSO) etc.Wherein, preferred diethylene glycol ethyl-methyl ether, propylene glycol methyl ether acetate, cyclopentanone and N-N-methyl-2-2-pyrrolidone N-.
These organic solvents (B) can distinguish independent use or combination is used two or more.The use amount of organic solvent (B) with respect to resin 100 weight portions usually 20 ~ 10, the scope of 000 weight portion, preferably 50 ~ 5, the scope of 000 weight portion, more preferably 100 ~ 1, the scope of 000 weight portion.
Use among the present invention resin combination in, preferably also contain compound (C) with acidic-group.Not special qualification of compound (C) with acidic-group, preferred fat compounds of group, aromatic compound, heterocyclic compound, further preferred fragrance compounds of group, heterocyclic compound.These compounds (C) can distinguish independent use or combination is used two or more.
The acidic-group number is not special to be limited, and preferably has two above acidic-groups, especially preferably has two acidic-groups.Can be the same or different between the acidic-group.
Acidic-group is that acid functional group gets final product, and as its concrete example, can enumerate: strong acid groups such as sulfonic group, phosphate; Faintly acid groups such as carboxyl, mercapto and carboxyl methylene sulfenyl.Wherein, preferred carboxyl, mercapto or carboxyl methylene sulfenyl, preferred especially carboxyl.In addition, in these acidic-groups, preferred acid dissociation constant pKa is more than 3.5 and the group of 5.0 following scopes.In addition, under situation, the first dissociation constant pKa1 is made as acid ionization constant with two above acidic-groups.Need to prove that as far as pKa, under the dilute aqueous solution condition, acid ionization constant Ka is [H 3O +] [B -]/[BH].At this, BH representes organic acid, B -Expression organic acid conjugate base.PKa is pKa=-logKa.In addition, as far as the assay method of pKa, for example can use pH meter to measure hydrogen ion concentration and calculate pKa by the concentration and the hydrogen ion concentration of this material.
In the present invention, owing to use the compound (C) with these acidic-groups, the passivating film that is formed by resin combination of the present invention is in excellence aspect the reliability that improves thin-film transistor.
In the present invention, above-claimed cpd (C) can have the substituting group beyond the acidic-group.As such substituting group, can enumerate: alkyl such as alkyl, aryl; And, halogen atom; Alkoxyl, aryloxy group, acyloxy, heterocyclic oxy group; Amino by alkyl or aryl or the substituted amino of heterocyclic radical, acyl amino, urea groups, aminosulfonyl amino, alkoxycarbonyl amino, aryloxycarbonyl; Alkylthio group, arylthio, heterocycle sulfenyl etc. do not have the polar group of proton and are not had the substituted alkyl of polar group institute etc. of proton by these.
As the concrete example of compound (C), can enumerate: formic acid, acetate, propionic acid, butyric acid, valeric acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, glycolic, glyceric acid, ethanedioic acid (being also referred to as " oxalic acid "), propane diacid (being also referred to as " malonic acid "), succinic acid (being also referred to as " butanedioic acid "), glutaric acid, hexane diacid (being also referred to as " adipic acid "), 1,2-cyclohexane dicarboxylic acid, 2 hydroxy propanoic acid, 2-hydroxysuccinic acid, 2-hydroxy propane tricarboxylic acids, mercapto succinic acid, dimercaptosuccinic acid, 2; 3-dimercapto-1-propyl alcohol, 1,2,3-tri-thiol propane, 2; 3,4-tri-thiol-1-butanols, 2,4-dimercapto-1; 3-butanediol, 1; 3,4-tri-thiol-2-butanols, 3,4-dimercapto-1; 2-butanediol, 1,5-dimercapto-3-ethyl sulfide aliphatic compounds such as (thiapentane); Benzoic acid, P-hydroxybenzoic acid, septichen, 2-naphthalene-carboxylic acid, methyl benzoic acid, mesitylenic acid, trimethylbenzoic acid, 3-phenylpropionic acid, 2 hydroxybenzoic acid, dihydroxy-benzoic acid, dimethoxybenzoic acid, benzene-1,2-dicarboxylic acids (being also referred to as " phthalic acid "), benzene-1,3-dicarboxylic acids (being also referred to as " M-phthalic acid "), benzene-1,4-dicarboxylic acids (being also referred to as " terephthalic acid (TPA) "), benzene-1; 2,3-tricarboxylic acids, benzene-1,2,4-tricarboxylic acids, benzene-1; 3,5-tricarboxylic acids, benzene hexacarboxylic acid, biphenyl-2,2 '-dicarboxylic acids, 2-(carboxyl methyl) benzoic acid, 3-(carboxyl methyl) benzoic acid, 4-(carboxyl methyl) benzoic acid, 2-(carboxyl carbonyl) benzoic acid, 3-(carboxyl carbonyl) benzoic acid, 4-(carboxyl carbonyl) benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, 2-sulfydryl-6-naphthalene-carboxylic acid, 2-sulfydryl-7-naphthalene-carboxylic acid, 1,2-thioresorcin, 1; 3-thioresorcin, 1,4-thioresorcin, 1,4-naphthyl disulfide alcohol, 1,5-naphthyl disulfide alcohol, 2; 6-naphthyl disulfide alcohol, 2,7-naphthyl disulfide alcohol, 1,2,3-tri-thiol benzene, 1; 2,4-tri-thiol benzene, 1,3,5-tri-thiol benzene, 1; 2,3-three (mercapto methyl) benzene, 1,2; 4-three (mercapto methyl) benzene, 1,3,5-three (mercapto methyl) benzene, 1; 2,3-three (mercaptoethyl) benzene, 1,2; 4-three (mercaptoethyl) benzene, 1,3, aromatic compounds such as 5-three (mercaptoethyl) benzene; Nicotinic acid, isonicotinic acid, 2-furancarboxylic acid, pyrroles-2,3-dicarboxylic acids, pyrroles-2,4-dicarboxylic acids, pyrroles-2; 5-dicarboxylic acids, pyrroles-3,4-dicarboxylic acids, imidazoles-2,4-dicarboxylic acids, imidazoles-2; 5-dicarboxylic acids, imidazoles-4; 5-dicarboxylic acids, pyrazoles-3,4-dicarboxylic acids, pyrazoles-3,5-dicarboxylic acids etc. contains the five member ring heterocyclic compound of nitrogen-atoms; Thiophene-2,3-dicarboxylic acids, thiophene-2,4-dicarboxylic acids, thiophene-2,5-dicarboxylic acids, thiophene-3,4-dicarboxylic acids, thiazole-2,4-dicarboxylic acids, thiazole-2; 5-dicarboxylic acids, thiazole-4,5-dicarboxylic acids, isothiazole-3,4-dicarboxylic acids, isothiazole-3,5-dicarboxylic acids, 1,2; 4-thiadiazoles-2,5-dicarboxylic acids, 1,3,4-thiadiazoles-2,5-dicarboxylic acids, 3-amino-5-sulfydryl-1; 2,4-thiadiazoles, 2-amino-5-sulfydryl-1,3,4-thiadiazoles, 3,5-dimercapto-1; 2,4-thiadiazoles, 2,5-dimercapto-1,3,4-thiadiazoles, 3-(5-sulfydryl-1; 2,4-thiadiazoles-3-base sulfonyl) butanedioic acid, 2-(5-sulfydryl-1,3,4-thiadiazoles-2-base sulfonyl) butanedioic acid, (5-sulfydryl-1,2; 4-thiadiazoles-3-base sulfenyl) acetate, (5-sulfydryl-1,3,4-thiadiazoles-2-base sulfenyl) acetate, 3-(5-sulfydryl-1,2,4-thiadiazoles-3-base sulfenyl) propionic acid, 2-(5-sulfydryl-1; 3,4-thiadiazoles-2-base sulfenyl) propionic acid, 3-(5-sulfydryl-1,2,4-thiadiazoles-3-base sulfenyl) butanedioic acid, 2-(5-sulfydryl-1,3; 4-thiadiazoles-2-base sulfenyl) butanedioic acid, 4-(3-sulfydryl-1,2,4-thiadiazoles-5-yl) sulfenyl butane sulfonic acid, 4-(2-sulfydryl-1,3,4-thiadiazoles-5-yl) sulfenyl fourth sulfonic acid etc. comprise the five member ring heterocyclic compound of nitrogen-atoms and sulphur atom; Pyridine-2,3-dicarboxylic acids, pyridine-2,4-dicarboxylic acids, pyridine-2,5-dicarboxylic acids, pyridine-2,6-dicarboxylic acids, pyridine-3; 4-dicarboxylic acids, pyridine-3,5-dicarboxylic acids, pyridazine-3,4-dicarboxylic acids, pyridazine-3,5-dicarboxylic acids, pyridazine-3; 6-dicarboxylic acids, pyridazine-4,5-dicarboxylic acids, pyrimidine-2,4-dicarboxylic acids, pyrimidine-2,5-dicarboxylic acids, pyrimidine-4; 5-dicarboxylic acids, pyrimidine-4,6-dicarboxylic acids, pyrazine-2,3-dicarboxylic acids, pyrazine-2,5-dicarboxylic acids, pyridine-2; 6-dicarboxylic acids, triazine-2,4-dicarboxylic acids, 2-diethylamino-4,6-dimercapto-secondary triazine, 2-dipropyl amino-4,6-dimercapto-secondary triazine, 2-dibutylamino-4; 6-dimercapto-secondary triazine, 2-anilino--4,6-dimercapto-secondary triazine, 2,4,6-tri-thiol-secondary triazine etc. contains the 6-membered heterocyclic compound of nitrogen-atoms.Wherein, consider that from the viewpoint that has good stability that further makes thin-film transistor the acidic-group number is preferably more than two, is preferably two especially.
As compound with two acidic-groups, preferred ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, 1,2-cyclohexane dicarboxylic acid, benzene-1; 2-dicarboxylic acids (being also referred to as " phthalic acid "), benzene-1,3-dicarboxylic acids (being also referred to as " M-phthalic acid "), benzene-1,4-dicarboxylic acids (being also referred to as " terephthalic acid (TPA) "), biphenyl-2; 2 '-dicarboxylic acids, 2-(carboxyl methyl) benzoic acid, 3-(carboxyl methyl) benzoic acid, 4-(carboxyl methyl) benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, 2-sulfydryl-6-naphthalene-carboxylic acid, 2-sulfydryl-7-naphthalene-carboxylic acid, 1; 2-thioresorcin, 1,3-thioresorcin, 1,4-thioresorcin, 1; 4-naphthyl disulfide alcohol, 1; 5-naphthyl disulfide alcohol, 2,6-naphthyl disulfide alcohol, 2,7-naphthyl disulfide alcohol etc. has the aromatic compound of two acidic-groups; Pyrroles-2,3-dicarboxylic acids, pyrroles-2,4-dicarboxylic acids, pyrroles-2,5-dicarboxylic acids, pyrroles-3,4-dicarboxylic acids, imidazoles-2, the 4-dicarboxylic acids-, imidazoles-2; 5-dicarboxylic acids, imidazoles-4,5-dicarboxylic acids, pyrazoles-3,4-dicarboxylic acids, pyrazoles-3,5-dicarboxylic acids, thiophene-2,3-dicarboxylic acids, thiophene-2,4-dicarboxylic acids, thiophene-2; 5-dicarboxylic acids, thiophene-3,4-dicarboxylic acids, thiazole-2,4-dicarboxylic acids, thiazole-2,5-dicarboxylic acids, thiazole-4,5-dicarboxylic acids, isothiazole-3; 4-dicarboxylic acids, isothiazole-3,5-dicarboxylic acids, 1,2,4-thiadiazoles-2,5-dicarboxylic acids, 1; 3,4-thiadiazoles-2,5-dicarboxylic acids, (5-sulfydryl-1,2,4-thiadiazoles-3-base sulfenyl) acetate, (5-sulfydryl-1; 3,4-thiadiazoles-2-base sulfenyl) acetate, pyridine-2,3-dicarboxylic acids, pyridine-2,4-dicarboxylic acids, pyridine-2,5-dicarboxylic acids, pyridine-2; 6-dicarboxylic acids, pyridine-3,4-dicarboxylic acids, pyridine-3,5-dicarboxylic acids, pyridazine-3,4-dicarboxylic acids, pyridazine-3,5-dicarboxylic acids, pyridazine-3; 6-dicarboxylic acids, pyridazine-4,5-dicarboxylic acids, pyrimidine-2,4-dicarboxylic acids, pyrimidine-2,5-dicarboxylic acids, pyrimidine-4,5-dicarboxylic acids, pyrimidine-4; 6-dicarboxylic acids, pyrazine-2,3-dicarboxylic acids, pyrazine-2,5-dicarboxylic acids, pyridine-2,6-dicarboxylic acids, triazine-2,4-dicarboxylic acids etc. has the heterocyclic compound of two acidic-groups.
Through using these compounds, can obtain following effect: make the stability of thin-film transistor better with the organic passivation film that forms by resin combination.
The content of the compound with acidic-group (C) in the resin combination that uses among the present invention with respect to resin (A) 100 weight portions usually in the scope of 1 ~ 45 weight portion, preferably in the scope of 1.5 ~ 30 weight portions, further preferably in the scope of 2 ~ 15 weight portions.The use amount of compound (C) with acidic-group is when this scope; Even after manufacturing, the resin combination that obtains is preserved; The characteristic of resin combination can not change because of the rerum natura of resin combination, can obtain the excellent resin combination of liquid stability.
The preferred further inclusion compound (D) of the resin combination that uses among the present invention, this compound (D) have and are selected from a kind of atom in silicon atom, titanium atom, aluminium atom and the zirconium atom and have oxyl or the hydroxyl that is bonded to this atom.
And then, in the above-claimed cpd (D), preferably have the compound of the oxyl that is bonded to silicon atom or titanium atom.In addition, above-mentioned oxyl is preferably the oxyl of carbon number 1 ~ 18.
In addition, as far as compound (D), when resin (A) had the protic polar group, preferred especially its had the functional group that can react with the protic polar group.Functional group's preferred isocyanate base, sulfydryl, epoxy radicals or amido that this can react with the protic polar group, further preferred epoxy radicals.
Concrete example as compound (D); Can enumerate: tetraalkoxysilane classes such as tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, MTMS, MTES, ethyl trimethoxy silane, ethyl triethoxysilane, n-pro-pyl trimethoxy silane, n-pro-pyl triethoxysilane, isopropyl trimethoxy silane, isopropyl triethoxysilane, normal-butyl trimethoxy silane, ne-butyltriethoxysilaneand, n-pentyl trimethoxy silane, n-hexyl trimethoxy silane, n-heptyl trimethoxy silane, n-octyl trimethoxy silane, positive decyl trimethoxy silane, styryl trimethoxy silane, vinyltrimethoxy silane, VTES, cyclohexyl trimethoxy silane, cyclohexyl trimethoxy silane, cyclohexyl triethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-chloropropyl triethoxysilane, 3; 3; 3-trifluoro propyl trimethoxy silane, 3; 3; 3-trifluoro propyl triethoxysilane, 3-TSL 8330,3-aminopropyltriethoxywerene werene, N-2-(amino-ethyl)-3-TSL 8330, N-phenyl-3-TSL 8330,2-hydroxyethyl trimethoxy silane, 2-hydroxyethyl triethoxysilane, 2-hydroxypropyl trimethoxy silane, 2-hydroxypropyl triethoxysilane, 3-hydroxypropyl trimethoxy silane, 3-hydroxypropyl triethoxysilane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, 3-isocyanates propyl trimethoxy silicane, 3-isocyanates propyl-triethoxysilicane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 2-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3; The 4-epoxycyclohexyl) compound of silicon atoms such as dialkoxy silicane class such as trialkoxysilanes, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyl dimethoxy silane, diethyl diethoxy silane, di dimethoxy silane, di diethoxy silane, diisopropyl dimethoxy silane, diisopropyl diethoxy silane, di-n-butyl dimethoxy silane, two n-pentyl dimethoxy silane, two n-pentyl diethoxy silanes, di-n-hexyl dimethoxy silane, di-n-hexyl diethoxy silane, two n-heptyl dimethoxy silane, two n-heptyl diethoxy silanes, di-n-octyl dimethoxy silane, di-n-octyl diethoxy silane, two positive cyclohexyl dimethoxy silane, two positive cyclohexyl diethoxy silanes, dimethoxydiphenylsilane, diphenyl diethoxy silane, 3-glycidoxy propyl group methyldiethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-acryloxy propyl group methyl dimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-acryloxy propyl group methyldiethoxysilane, N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilanes such as ethyl triethoxysilane, 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, 3-ethyl (trimethoxysilyl propoxyl group methyl) oxetanes, 3-ethyl (triethoxysilyl propoxyl group methyl) oxetanes, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) propyl group amine, two (triethoxysilylpropyltetrasulfide) four thioethers and methyl triacetoxysilane, dimethyl diacetoxy silane, trade name X-12-414, KBP-44 (Shin-Etsu Chemial Co., Ltd's system), 217FLAKE, 220FLAKE, 233FLAKE, z6018 (eastern beautiful DOW CORNING Co., Ltd. system); (tetraisopropoxy titanium; Four titanium n-butoxide; Four (2-Ethylhexyl Alcohol) titanium; The isopropoxy octylene glycol titanate; Diisopropoxy two (acetylacetone,2,4-pentanedione) closes titanium; The third dioxy base titanium two (ethyl acetoacetate); Monostearate three titanium n-butoxide; Distearyl acid diisopropoxy titanium; The stearic acid titanium; Two isostearic acid diisopropoxy titaniums; (2-n-butoxy carbonyl benzoyl oxygen base) three titanium butoxide; (triethanolamine acid group) two normal propyl alcohol titaniums and PLENACT series (aginomoto fine chemistry Co., Ltd. system)) titaniferous atomic compound such as; (acetyl alkoxyl diisopropyl acid aluminium) etc. contains the aluminium atomic compound; (four n-propoxyzirconium, four n-butoxy zirconiums, four acetyl acetone zirconiums, three butoxy acetyl acetone zirconiums, only son's oxygen ethylacetoacetone two (ethyl acetoacetate) are closed zirconium, dibutoxy two (ethyl acetoacetate) closes zirconium, four acetyl acetone zirconiums, stearic acid three butoxy zirconiums) etc. contains the zirconium atom compound.
As above-claimed cpd (D), preferred silicon atoms compound, titaniferous atomic compound wherein especially preferably has the functional group that can react with the protic polar group.Through having above-mentioned functional group, make the stability of thin-film transistor better.
As compound with the functional group that can react with above-mentioned protic polar group; Preferred especially 3-TSL 8330,3-aminopropyltriethoxywerene werene, N-2-(amino-ethyl)-3-TSL 8330, N-phenyl-3-TSL 8330,3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, 3-isocyanates propyl trimethoxy silicane, 3-isocyanates propyl-triethoxysilicane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 2-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3; The 4-epoxycyclohexyl) ethyl triethoxysilane, 3-urea groups propyl trimethoxy silicane, 3-urea groups propyl-triethoxysilicane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) propylamine, N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane.These compounds (D) can be used alone or in combination two or more respectively.
Compound (D) content that is used for resin combination of the present invention is with respect to the scope of adhesive resin (A) 100 weight portions at 1 ~ 40 weight portion, preferably in the scope of 3 ~ 30 weight portions, more preferably in the scope of 5 ~ 25 weight portions.The use amount of compound (D) can make the stability of thin-film transistor better when this scope.
Be used for resin combination of the present invention, preferably further containing radioactive ray sensitive compound (E) and form.
The radioactive ray sensitive compound (E) that uses among the present invention is through causing the compound of chemical reaction behind irradiation ultraviolet radiation or the electron beam isoradial.In the present invention, radioactive ray sensitive compound (E) preferably can be controlled the deliquescent compound of alkali of the resin molding that is formed by resin combination.
In the present invention, preferably use photoacid generator as radioactive ray sensitive compound (E).
As radioactive ray sensitive compound (E), for example can enumerate: acetophenone compound, triaryl sulfonium salts, triazo-compounds such as quinone di-azido compound etc., preferred triazo-compound, preferred especially quinone di-azido compound.
As quinone di-azido compound, the ester compounds that for example can use quinone two nitrine sulfonic acid halides and compound to form with phenol property hydroxyl.As the concrete example of quinone two nitrine sulfonic acid halides, can enumerate: 1,2-naphthoquinones two nitrine-5-sulfonic acid chloride, 1,2-naphthoquinones two nitrine-4-sulfonic acid chloride, 1,2-benzoquinones two nitrine-5-sulfonic acid chloride etc.As the typical example of compound, can enumerate with phenol property hydroxyl: 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane, 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol etc.
As the compound beyond these, can enumerate: 2,3 with phenol property hydroxyl; 4-trihydroxybenzophenone, 2,3,4; 4 '-tetrahydroxybenzophenone, two (4-hydroxy phenyl) propane, three (4-hydroxy phenyl) methane, 1,1 of 2-, 1-three (4-hydroxy-3-methyl phenyl) ethane, 1; 1,2,2-four (4-hydroxy phenyl) ethane, the oligomer of phenolic resins, the compound that will have an above phenol property hydroxyl and bicyclopentadiene carry out copolymerization and oligomer of obtaining etc.
Wherein, preferred 1,2-naphthoquinones two nitrine-5-sulfonic acid chloride and condensation product with compound of phenol property hydroxyl; More preferably 1,1,3-three (2; 5-dimethyl-4-hydroxy phenyl)-and 3-phenyl-propane (1 mole) and 1, the condensation product of 2-naphthoquinones two nitrine-5-sulfonic acid chloride (2.5 moles).
As photoacid generator; Except that quinone di-azido compound; Can use salt, halogenated organic compounds, α; α '-two (sulfonyl) diazomethane compounds, alpha-carbonyl-α '-sulfonyl diazomethane compounds, known materials such as sulphones, organic acid esters compound, organic acid amide compound, organic acid imide compound.
These radioactive ray sensitive compounds can distinguish independent use or combination is used two or more.Radioactive ray sensitive compound (E) content that is used for resin combination of the present invention is with respect to the scope of resin (A) 100 weight portions at 1 ~ 100 weight portion, preferably in the scope of 5 ~ 50 weight portions, more preferably in the scope of 10 ~ 40 weight portions.The use amount of radioactive ray sensitive compound (E) is if in this scope; When then the resin molding that comprises resin combination on will being formed at any substrate carries out patterning; Radiation exposure portion and the radioactive ray not poor solubility of irradiating part in developer solution become big; Carry out patterning through development easily, and radioactive ray sensitivity uprises also, so preferred.
In the present invention, as the composition of resin combination, preferably further contain crosslinking agent (F).As crosslinking agent (F), can use the material that in molecule, has more than two, preferably has more than three functional group that can react with resin (A).Crosslinking agent (F) is as long as the functional group that is had can not react just not special with functional group in the adhesive resin or unsaturated bond etc. to be limited, the group that preferably can react with the protic polar group.
As this functional group, for example can enumerate: amino, hydroxyl, epoxy radicals, NCO etc., more preferably amino, epoxy radicals and NCO further are preferably epoxy radicals.
As the concrete example of crosslinking agent (F), can enumerate: aliphatic polyamine classes such as hexamethylene diamine; 4, aromatic polyamine classes such as 4 '-diaminodiphenyl ether, DADPS; 2, two (the 4 '-phenylazide methylene) cyclohexanone, 4 of 6-, nitrine classes such as 4 '-two nitrine diphenyl sulphone (DPS)s; Nylon, poly terephthalic acid 1, gather M-phthalic acid 1 at the 6-adipamide, and 6-hexamethylene diamine etc. are polyamide-based; N, N, N ', N ', N ", N " melamine class such as-six (alkoxy methyl) melamine; N, N ', N ", N " glycoluril class such as '-four (alkoxy methyl) glycoluril; Acrylate compounds such as ethylene glycol bisthioglycolate (methyl) acrylic acid ester; Isocyanate ester compounds such as hexamethylene diisocyanate class polyisocyanates, IPDI class polyisocyanates, toluene di-isocyanate(TDI) class polyisocyanates, hydrogenated diphenyl methane diisocyanate; 1,4-two (hydroxymethyl) cyclohexane, 1,4-two (hydroxymethyl) norbornane; 1,3,4-trihydroxy cyclohexane; Epoxy compoundss such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, polyphenol type epoxy resin, cyclic aliphatic epoxy resin, aliphatic glycidyl ether, epoxy acrylic ester polymer.
Concrete example as such epoxy compounds; Can enumerate: with the 3 functionality epoxy compoundss (trade name " XD-1000 ", Japanese chemical drug corporate system), [2 of bicyclopentadiene as skeleton; 1 of two (hydroxymethyl) 1-butanols of 2-; 2-epoxy-4-(2-Oxyranyle) cyclohexane addition product (15 functionality alicyclic epoxy resins, trade name " EHPE 3150 ", Daicel chemical industrial company system), epoxy-cyclohexene-1 with cyclohexane skeleton and terminal epoxy groups; The 6-caprolactone (aliphat ring-type 4 functionality epoxy resin, trade name " Epolead GT401 ", Daicel chemical industrial company system), 3 that the 6-caprolactone (aliphat ring-type 3 functionality epoxy resin, trade name " Epolead GT301 ", Daicel chemical industrial company system) that 2-dicarboxylic acids two (3-cyclohexenyl group methyl) is modified, epoxidation BTCA four (3-cyclohexenyl group methyl) are modified; 4-epoxide ring hexenyl methyl-3 ', 4 '-epoxide ring hexene carboxylate (trade name " CELLOXIDE 2021P ", Daicel chemical industrial company system) etc. has the epoxy compounds of alicyclic structure; Aromatic amine type multi-functional epoxy compound (trade name " H-434 "; Dongdu changes into industrial group's system); Cresols phenolic varnish type multi-functional epoxy compound (trade name " EOCN-1020 "; Japan's chemical drug corporate system); (EPICOAT 152 for phenol phenolic varnish type multi-functional epoxy compound; 154; The japan epoxy resin corporate system); Multi-functional epoxy compound (trade name EXA-4700 with naphthalene skeleton; Dainippon Ink and Chemicals, Inc's system); Chain-like alkyl multi-functional epoxy compound (trade name " SR-TMP "; This pharmaceutical industries of slope corporate system); Multi-functional epoxy's polybutadiene (trade name " Epolead PB3600 "; Daicel chemical industrial company system); The glycidyl polyether compound of glycerine (trade name " SR-GLG "; This pharmaceutical industries of slope Co., Ltd. system); Two glycerine polyglycidyl ether compound (trade names " SR-DGE "; This pharmaceutical industries of slope Co., Ltd. system); Poly-glycerine polyglycidyl ether compound (trade name " SR-4GL "; This pharmaceutical industries of slope Co., Ltd. system) etc. the epoxy compounds that does not have alicyclic structure.
Wherein, preferred epoxy compounds more preferably has the epoxy compounds of alicyclic structure, because it can make the stability of the thin-film transistor with the organic passivation film that is formed by this resin combination better.
The molecular weight of crosslinking agent (F) is not special to be limited, and is generally 100 ~ 100,000, is preferably 500 ~ 50,000, and more preferably 1,000 ~ 10,000.Crosslinking agent can distinguish independent use or combination is used two or more.
The content of crosslinking agent (F) that is used for resin combination of the present invention with respect to resin (A) 100 weight portions usually in the scope of 0.1 ~ 200 weight portion, preferably in the scope of 1 ~ 150 weight portion, more preferably in the scope of 5 ~ 100 weight portions.The use amount of crosslinking agent can obtain sufficient thermal endurance when this scope, so preferred.
Can be as required in the scope of not damaging effect of the present invention, resin combination of the present invention contains emulsion, surfactant, other compounding ingredients such as acid producing agent, oxidation inhibitor, light stabilizer, antifoaming agent, pigment, dyestuff etc. of diving being used for.
Concrete example as emulsion; Can enumerate: 2H-pyrido (3; 2-b)-1; 4 oxazines-3 (4H)-ketone, 10H-pyrido-(3,2-b)-1,4-benzo thiazides, urazole class, hydantoins, malonyl urea acids, glycine anhydride class, I-hydroxybenzotriazole class, alloxan class, maleimide etc.
In the present invention, preferably contain surfactant as the resin combination composition.
Start from purposes such as preventing striped (coating streak), raising development property and use surfactant.As its concrete example, can enumerate: polyoxyethylene alkyl ether classes such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as NONIN HS 240, polyoxyethylene nonylplenyl ether; Nonionic class surfactants such as the two alkyl esters of polyoxyethylene such as polyethylene glycol bilaurate, polyethylene glycol stearate diester; Fluorine class surfactant; Silicone based surfactant; Methacrylic acid copolymer class surfactant; Acrylic copolymer class surfactant etc.
Used latent acid producing agent from the purpose of thermal endurance that improves resin combination of the present invention and chemical proofing.As its concrete example, can enumerate acidic cationic polymerization catalyst through heating.Can enumerate: sulfosalt, benzothiazolium salt, ammonium salt, microcosmic salt etc.Wherein, preferred sulfosalt and benzothiazolium salt.
As oxidation inhibitor, can use the phenol that is used for common polymer is oxidation inhibitor, Phosphorus oxidation inhibitor, sulphur class oxidation inhibitor, lactone oxidation inhibitor etc.For example: as phenol, can enumerate: 2,6 di tert butyl 4 methyl phenol, p methoxy phenol; Styrenated phenol, n-octadecane base-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester, 2; 2 '-methylene-two (4-methyl-6-tert butyl phenol), the 2-tert-butyl group-6-(3 '-tert-butyl group-5 '-methyl-2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylic acid ester, 4; 4 '-butylidene-two-(3 methy 6 tert butyl phenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol); Pentaerythrite four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], alkylation bis-phenol etc.As phosphorous antioxidant, can enumerate triphenyl phosphite and tricresyl phosphite (nonyl phenyl) ester, be oxidation inhibitor as sulphur, can enumerate dilauryl thiodipropionate etc.
In the present invention, preferably contain light stabilizer as the resin combination composition.Light stabilizer can be caught the arbitrary substance in the material etc. of the free radical that is produced by light for ultra-violet absorbers such as benzophenone, salicylate class, benzotriazole, cyanoacrylate, metal complex salt, hindered amines (HALS) etc.Wherein, HALS is the compound with piperidine structure, to the less painted of the present composition and have good stability, so preferred.As concrete compound, can enumerate: two (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1; 2,2,6,6-pentamethyl-4-piperidyl/tridecyl 1,2; 3,4-butane tetracarboxylic acid esters, two (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate etc.
The preparation method who is used for resin combination of the present invention is not special to be limited, and utilizes each constituent of known method blended resin composition, and promptly resin (A) and organic solvent (B) and other composition of using according to expectation get final product.
Mixed method is not special to be limited, preferably with each constituent dissolving of resin combination or be dispersed in the organic solvent (B) and obtain solution or dispersion liquid mixes.Thus, the form with solution or dispersion liquid obtains resin combination of the present invention.
The method that will be used for each constituent dissolving of resin combination of the present invention or be dispersed in organic solvent (B) adopts common method to get final product.Particularly, can use the stirring of having adopted stirrer and magnetic agitation to carry out, high speed homogenization device, disperser (dispar), planetary stirrer, double-shaft mixers, ball mill, three-roller etc. to carry out.In addition, after the dissolving of each composition or being dispersed in the organic solvent (B), for example can use the filter about the 0.5 μ m of aperture etc. to filter.
Solid component concentration in the time of will being used for each constituent dissolving of resin combination of the present invention or being dispersed in organic solvent (B) is generally 1 ~ 70 weight %, is preferably 5 ~ 60 weight %, more preferably 10 ~ 50 weight %.Solid component concentration can make steady dissolution property, to film thickness uniformity, the flatness equal altitudes balance of the coating and the formed resin molding of substrate when this scope.
In the present invention, on having the substrate of thin-film transistor, form after the passivating film, it is crosslinked that this passivating film is taken place, and above-mentioned thin-film transistor obtains through the operation of the oxide-film of the semiconductor layer surface of removing channel region.
The crosslinked of passivating film that is formed on the aforesaid substrate can carry out through the cross-linking reaction of resin (A), preferably uses crosslinking agent.Crosslinked kind according to crosslinking agent selects suitable method to get final product, and carries out through heating usually.Heating means for example can be used hot plate, baking oven to wait to carry out.Heating-up temperature is generally 180 ~ 250 ℃, and wait come suitable select according to the equipment of size, thickness and the use of passivating film heating time, for example under the situation of using hot plate, usually 5 ~ 90 minutes scope; Using under the situation of baking box, usually 30 ~ 120 minutes scope.Heating also can be carried out under inactive gas atmosphere as required.As inactive gas, need only oxygen-free and can not make the passivating film oxidation, for example can enumerate: nitrogen, argon, helium, neon, xenon, krypton etc.Wherein, preferred nitrogen and argon, special preferred nitrogen.Special preferred oxygen content is the inactive gas below the 0.1 volume %, below the preferred 0.01 volume %, special preferred nitrogen.These inactive gass can distinguish independent use or combination is used two or more.
In the present invention, above-mentioned passivating film can be patterned.On the substrate patterning of formed passivating film for example can through as inferior method carry out: photoresist is carried out the method for dry-etching or makes resin combination contain the radiation-sensitive material as mask, use active radioactive ray on the resin molding that uses this resin combination to form, to form the sub-image pattern and use developer solution to make sub-image pattern method for visualizing etc.
As active radioactive ray, the ray that changes the alkali-soluble of the crosslinkable composite that contains photoacid generator so long as can make the photoacid generator activation gets final product, and does not have special qualification.Particularly, can use the light such as ultraviolet ray, KrF PRK, ArF PRK of single wavelengths such as ultraviolet ray, g ray and i ray; Like particle beams of electron beam and so on etc.As these active radioactive ray are optionally shone into pattern-like and form the sub-image method of patterning; The employing common method gets final product, and for example can use following method: utilize method that reduced projection exposure device etc. describes via the method for the light such as mask pattern irradiation ultraviolet radiation, g ray, i ray, KrF PRK and ArF PRK of expectation or through particles beams such as electron beams etc.Using under the situation of light as active radioactive ray, can adopt single wavelength light, also can adopt mixed wavelengths light.Illuminate condition can be selected according to the active radioactive ray that use are suitable, and for example when using the light of wavelength 200 ~ 450nm, exposure is usually 10 ~ 1,000mJ/cm 2Scope, preferably at 50 ~ 500mJ/cm 2Scope, confirm according to irradiation time and illumination.After as above shining active radioactive ray, as required, under the temperature about 60 ~ 130 ℃ resin molding was carried out heat treated about 1 ~ 2 minute.
Then, formed sub-image pattern on the passivating film is developed and it is manifested.In the present invention, such operation is called " patterning ", patterned passivating film is called " patterning passivating film ".As developer solution, can use the aqueous solution of alkali compounds usually.As alkali compounds, for example can use: alkali metal salt, amine and ammonium salt.Alkali compounds can also can be organic compound for inorganic compound.As the concrete example of these compounds, can enumerate: alkali metal salts such as NaOH, potassium hydroxide, sodium carbonate, sodium metasilicate, sodium metasilicate; Ammoniacal liquor; Primary amine such as ethamine, n-pro-pyl amine; Secondary amine such as diethylamine, di-n-propyl amine; Tertiary amine such as triethylamine, methyl-diethyl-amine; Quaternary ammonium salts such as TMAH, tetraethyl ammonium hydroxide, TBAH, choline; Hydramine such as dimethylethanolamine, triethanolamine; Pyrroles, piperidines, 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene, 1, cyclic amine such as 5-diazabicyclo [4.3.0] ninth of the ten Heavenly Stems-5-alkene, N-methyl pyrrolidone etc.These alkali compounds can distinguish independent use or combination is used two or more.
As the aqueous medium of buck property solution, can make water; Water-miscible organic solvent such as methyl alcohol, ethanol.The solution that buck property solution can form for the surfactant that adds appropriate amount etc.
As the method that developer solution is contacted with the passivating film with sub-image pattern, for example can use blade paddling process (パ De Le method), spray-on process, infusion process etc.Usually 0 ~ 100 ℃ scope, preferably 5 ~ 55 ℃ scope, more preferably 10 ~ 30 ℃ scope, developing time can suit to select in 30 ~ 180 seconds scope development temperature usually.
After as above forming the target pattern passivating film, for remove on the substrate, the development residue of substrate back and substrate end, can wash substrate with flushing liquor as required.Flushing utilizes compressed air or compressed nitrogen to remove residual flushing liquor after handling.
And then, in order to make the photoacid generator inactivation, also can be as required to the active radioactive ray of the substrate WBR with patterning passivating film.In order to shine active radioactive ray, illustrative method in the time of can utilizing the formation of above-mentioned sub-image pattern.Also can heat passivating film in irradiation or after the irradiation.As heating means, for example can enumerate: the method for utilizing heating plate or in baking oven, substrate being heated.Temperature is usually 100 ~ 300 ℃ scope, preferably 120 ~ 200 ℃ scope.
In the present invention, can after forming patterned resin on the substrate, carry out the cross-linking reaction of patterned resin.The crosslinked of formed passivating film likewise gets final product on crosslinked and the aforesaid substrate.
According to the manufacturing approach of semiconductor element substrate of the present invention, can make the high semiconductor element substrate of a kind of reliability.
The thin-film transistor that obtains through manufacturing approach of the present invention can be used for display unit such as active matrix-type liquid crystal display device and active matrix organic EL.In addition, the passivating film of the semiconductor element of making through manufacturing approach of the present invention is smooth, therefore, in display unit, can seek to improve brightness.In addition, can seek to reduce power consumption.In addition, can seek to improve the life-span of thin-film transistor.
In addition, containing the passivating film that organic material forms is low-k, therefore, can suppress RC and postpone.
Embodiment
Below, enumerate embodiment and comparative example is explained the present invention more specifically.Short of special instruction, " part " in each example reach " % " and are respectively " weight portion " and reach " weight % ".
Through following method each characteristic is estimated.
(1) tft characteristics
Use analyzing parameters of semiconductor appearance (Agilent corporate system 4156A) that the mensuration after the firm making is measured with the variation that the grid voltage variation produces with the source electrode electric leakage electrode current of sample (substrate with thin-film transistor).Between source electrode and drain electrode, apply the voltage of 10V, the minimum value of source electrode electric leakage electrode current is made as the off-state leakage current value and observes when will be in the scope of-10V ~ 15V changing grid voltage with each 0.2V.Then, be arranged in the constant temperature and humidity cabinet (ESPEC corporate system Platinus PR-2KP) that is set at 60 ℃ of temperature, humidity 90% with sample measuring.After being provided with, through said method the off-state leakage current value was measured up to 100 hours in per 20 hours, surpass 100 hours after, through said method the off-state leakage current value was measured in per 100 hours, the off-state leakage current value is arrived 1.0 * 10 -11The time of A is observed as tft characteristics.Analyze according to this, can know that the reliability of the long more thin-film transistor of tft characteristics is high more.
(making example 1)
Will be by N-(2-ethylhexyl)-dicyclo [2.2.1] heptan-5-alkene-2,40 moles of % of 3-dicarboxyl acid imide (NEHI) and 8-hydroxycarbonyl group Fourth Ring [4.4.0.1 2,5.1 7,10] 100 parts of the monomer mixtures that constitute of 60 moles of % of 12 carbon-3-alkene (TCDC), 1; 2 parts of 5-hexadienes, chlorine (1; 3-methylimidazole quinoline-2-subunit) (tricyclohexyl phosphine) benzal ruthenium is (through Org.Lett.; The 1st volume, 953 pages, the method put down in writing in 1999 synthesize) in the glass voltage-resistant reactor after 0.02 part and 400 parts of nitrogen displacements of packing into of diethylene glycol methyl ethyl ether, stir on one side it reacted 4 hours, obtain polymerization liquid.Then, the polymerization liquid that obtains is added in the autoclave, 150 ℃, hydrogen pressure 4MPa down stirring carried out hydrogenation in 5 hours, obtain cyclic olefin resin solution thus.The polymerisation conversion of the cyclic olefin resin in the solution that obtains is 99.7%, and weight average molecular weight is 7150, and number-average molecular weight is 4690, and molecular weight distribution is 1.52, and hydrogenation ratio is 99.7%.
Then; In the cyclic olefin resin solution that as above obtains (cyclic olefin resin in the solution is 100 parts a amount), add as pyrazine-2 with compound of acidic-group; 2 parts of 3-dicarboxylic acids, as 1 of radioactive ray sensitive compound; 1; 3-three (2; 5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane (1 mole) and 1; 30 parts of the condensation products of 2-naphthoquinones two nitrine-5-sulfonic acid chloride (2 moles) (Japan's compound probability corporate system " TS200 "), as 30 parts of the methyl-etherified melmacs (Cytec Industries corporate system " Cymel 370 ") of crosslinking agent; 3,4-epoxide ring hexenyl methyl-3 ', 10 parts of the 6-caprolactones (Daicel chemical industrial company system " Epolead GT401 ") that 30 parts of 4 '-epoxide ring hexene carboxylates (Daicel chemical industrial company system " CELLOXIDE 2021P ") and epoxidation BTCA four (3-cyclohexenyl group methyl) are modified, [3-(3 as the pentaerythrite four of oxidation inhibitor; The 5-di-tert-butyl-hydroxy phenyl) propionic ester] (Ciba Specialty Chemicals corporate system " rganox 1010 ") 1 part and be the silicone based surfactant (silicone of SHIN-ETSU HANTOTAI corporate system " KP-341 ") of 300ppm amount as the concentration in the solution of surfactant, add 100 parts of diethylene glycol methyl ethyl ethers again and mix and stir.Stir after 30 minutes, use the polytetrafluoroethylene filter made device of aperture 0.45 μ m that this solution is filtered, preparation contains cyclic olefin resin and has the resin combination (α) of radiation-sensitive.
(making example 2)
With 30 parts of 20 parts of styrene, 25 parts of butyl methacrylates, 25 parts of 2-EHAs, methacrylic acid, 2; In the glass voltage-resistant reactor after 300 parts of nitrogen displacements of packing into of 0.5 part of 2-azodiisobutyronitrile and propylene glycol methyl ether acetate, under 80 ℃, make its reaction 4 hours when in nitrogen current, stirring.Then, concentrate the reaction solution that obtains through utilizing Rotary Evaporators, the solid component concentration with 35% obtains acrylic resin soln.The polymerisation conversion of the acrylic resin in the solution that obtains is more than 99%, and weight average molecular weight is 15000, and number-average molecular weight is 6500, and molecular weight distribution is 2.31.
Then; Add in the acrylic resin soln that as above obtains (amount when the acrylic resin in the solution is 100 parts) as have 10 parts of the 3-glycidoxypropyltrime,hoxysilane (eastern beautiful DOW CORNING Co., Ltd.'s system " SH-6040 ") of the compound that is bonded to the oxyl on the silicon atom, as 1 of radioactive ray sensitive compound; 1; 3-three (2; 5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane (1 mole) and 1; 30 parts of the condensation products of 2-naphthoquinones two nitrine-5-sulfonic acid chloride (2 moles) (Japan's compound probability corporate system " TS200 "), as 50 parts of the methyl-etherified melmacs (Cytec Industries corporate system " Cymel 350 ") of crosslinking agent, [3-(3 as the pentaerythrite four of oxidation inhibitor; The 5-di-tert-butyl-hydroxy phenyl) propionic ester] (Ciba Specialty Chemicals corporate system " Irganox 1010 ") 1 part and as the silicone based surfactant (amount when solution concentration is 300 ppm by weight) (silicone of SHIN-ETSU HANTOTAI corporate system " KP-341 ") of surfactant, add 100 parts of propylene glycol methyl ether acetates again and mix stirring.Stir after 30 minutes, utilize the polytetrafluoroethylene filter made device of aperture 0.45 μ m that this solution is filtered, preparation contains acrylic resin and has the resin combination (β) of radiation-sensitive.
(embodiment 1)
Go up the chromium film that forms as the thickness 200nm of gate electrode at glass substrate (Corning Incorporated, goods name Corning1737) through sputtering method.Then; For above-mentioned chromium film is carried out patterning and makes gate electrode; To be coated on the above-mentioned chromium film as the positive light anti-etching agent (Nippon Zeon Co., Ltd. makes ZPP-1800U3) of etching mask through spin-coating method, use hot plate to remove and desolvate, form the resist film of 1.5 μ m thus.Then, carry out exposure process and developing procedure, resist film is carried out patterning.Then, use cerium ammonium nitrate, form gate electrode thereby the chromium film is carried out patterning through Wet-type etching as etching solution.Then, use the mixed solution (MEA/DMSO=7/3) of MEA (MEA) and dimethyl sulfoxide (DMSO) (DMSO) to remove resist film as stripper.
Then, form covering grid electrode successively through the CVD method respectively and become the silicon nitride film of the thickness 450nm of gate insulating film, become semiconductor layer thickness 250nm a-Si layer (amorphous silicon layer) and become the n+Si layer of the thickness 50nm of the semiconductor layer that is added with impurity.Then; For above-mentioned semiconductor layer and the semiconductor layer pattern that is added with impurity are turned to island; To be coated on the semiconductor layer that is added with impurity and use hot plate to remove and desolvate as the positive light anti-etching agent of etching mask (ZPP-1800U3 that Nippon Zeon Co., Ltd. makes) through spin-coating method, form the resist film of 1.5 μ m thus.Then, through exposure process, developing procedure resist film is carried out patterning.The semiconductor layer and the semiconductor layer pattern that then, will be added with impurity through dry-etching turn to island.Then, use the mixed solution (MEA/DMSO=7/3) of MEA (MEA) and dimethyl sulfoxide (DMSO) (DMSO) to remove resist film as stripper.Then, utilizing hydrogen plasma to handle the hydrogen plasma that under the state of the bias voltage that applies 100W, carried out 5 minutes with device (Dipole Ring Magnet [Tokyo Electronics Inc.'s system] is modified to the device that can carry out Cement Composite Treated by Plasma) handles.Then, to carrying out 30 seconds flushing through the substrate to above-mentioned operation, the ultra-pure water that utilizes nitrogen when flushing, to adhere to is removed from substrate surface with ultra-pure water.Then, the above-mentioned resin combination (α) that will be used to form the passivating film that contains organic material through spin-coating method is coated on the substrate after the above-mentioned operation, and uses hot plate 90 ℃ of following heat dryings (prebake) 2 minutes, forms the resin molding of thickness 2.5 μ m.Then, the mask via the sectional hole patterns of 10 μ m * 10 μ m is 5mW/cm to this resin molding irradiation 365nm and luminous intensity in air 2Ultraviolet ray 40 seconds.Then, the tetramethylammonium hydroxide aqueous solution that uses 0.4 weight % after carrying out 90 seconds development treatment under 23 ℃, with ultra-pure water flushing 30 seconds, form the pattern of contact hole after, 230 ℃ of heating down (back oven dry) 60 minutes.Thus, obtain being formed with the thin-film transistor of patterned organic passivation film.
(embodiment 2)
In hydrogen plasma is handled, bias voltage is made as 0W, in addition, utilize the thin-film transistor that obtains being formed with patterned organic passivation film with embodiment 1 same method.
(embodiment 3)
Use resin combination (β) to replace resin combination (α), in addition, utilize the thin-film transistor that has obtained forming patterned organic passivation film with embodiment 2 same methods.
(comparative example 1)
Except that not carrying out hydrogen plasma handles, likewise make with embodiment 1 and to be formed with the thin-film transistor of patterned organic passivation film and to estimate.
(comparative example 2)
Passivating film is changed to through carrying out the silicon nitride film (SiNx film) of film forming with silane gas and ammonia as the CVD method of raw material, in addition, likewise make thin-film transistor with embodiment 1 and estimate.
(comparative example 3)
Except that not carrying out hydrogen plasma handles, likewise make thin-film transistor with comparative example 2 and estimate.
(comparative example 4)
Except that not carrying out hydrogen plasma handles, likewise make with embodiment 3 and to be formed with the thin-film transistor of patterned organic passivation film and to estimate.
In addition, in table 1, also shown the result that following characteristic is estimated.
(2) aperture opening ratio
Will except that wiring portion and the transistor portion can be through light the area of part with respect to the ratio of the area of the thin film transistor base plate of making as aperture opening ratio.Aperture opening ratio is high more, and brightness is more excellent.
(3) the passivating film production process number after TFT makes
Operation shown in (a) ~ Fig. 2 (c) that utilizes Fig. 1 made behind the thin-film transistor up to the needed operation number of thin-film transistor that obtains being formed with the patterning passivating film compare.
That is, in embodiment 1 ~ 3, need following six procedures: (i) hydrogen plasma handle, (ii) clean, (iii) coating, (iv) exposure, (v) develop, (vi) oven dry.
In addition, in comparative example 1 and 4, need following five processes: (i) cleaning, (ii) coating, (iii) exposure, (iv) development, (v) oven dry.
In addition, in comparative example 2, need following eight procedures: clean (i), (ii) utilize that the CVD method forms the SiNx film, (iii) cleans, (iv) coating, (v) exposure, (vi) develop, (vii) oven dry, (viii) dry-etching.
In addition, in comparative example 3, need following nine procedures: (i) hydrogen plasma handle, (ii) clean, (iii) utilize the CVD method form the SiNx film, (iv) clean, (v) coating, (vi) exposure, (vii) develop, (viii) oven dry, (ix) dry-etching.
(4) relative dielectric constant and RC postpone
After will making the resin combination of making in the example 1 and 2 that contains organic material and be coated on the silicon wafer through spin-coating method, use hot plate, form the resin molding of thickness 2.5 μ m 90 ℃ of following heat dryings (prebake) 2 minutes.Then, heated 60 minutes down, obtain using sample by the test that the silicon wafer that is formed with the resin molding that contains organic material constitutes at 230 ℃.
In addition, utilize with silane gas and ammonia and on silicon wafer, form silicon nitride film (SiNx film), use hot plate at 90 ℃ of following heat dryings (prebake) 2 minutes, the resin molding of formation thickness 120nm as the CVD method of raw material.Then, heated 60 minutes down, obtain using sample by the test that the silicon wafer that has formed the SiNx film constitutes at 230 ℃.Then, use the test that obtains to measure the relative dielectric constant of resin molding and SiNx film down at 10kHz (room temperature) with sample and according to JIS C6481.Relative dielectric constant is low more preferred more.
RC is postponed, in 65 inches full HD television set, input signal is made as 10V, calculate the data arrange end through following formula and reach the required time of 97% voltage, show as RC time of delay (DT).
V(t)=V(1-exp[t/RC])
V: input voltage, t: time, R: the resistance of data arrange, C: the parasitic capacity of data arrange
[table 1]
Figure BDA00001707784100351
Result by table 1 can know, characteristic can deterioration yet under the atmosphere of harshness even carry out that hydrogen plasma is handled and in passivating film, use the thin-film transistor that organic material is arranged, and reliability is very high.In addition, have with use that to contain organic and/or inorganic materials be that the substrate of the passivating film that forms of SiNx is compared, use the process number that the thin film transistor base plate that contains the passivating film that organic material forms is arranged few and can make easily.And then the aperture opening ratio of passivating film that contains organic material is high, and therefore, brightness is excellent, and then relative dielectric constant is low, can suppress RC and postpone.

Claims (5)

1. the manufacturing approach of a semiconductor element substrate, it comprises following operation:
Semiconductor component surfaces or the contained semiconductor layer surface of said semiconductor element are carried out the operation of Cement Composite Treated by Plasma;
On said semiconductor component surfaces of having carried out said Cement Composite Treated by Plasma or said semiconductor layer surface, form the operation of the passivating film that contains organic material.
2. the manufacturing approach of semiconductor element substrate according to claim 1, wherein, said Cement Composite Treated by Plasma is that hydrogen plasma is handled.
3. the manufacturing approach of semiconductor element substrate according to claim 1 and 2, wherein, said semiconductor element or said semiconductor layer are made through following operation, and said operation comprises:
On substrate, form the operation of gate electrode, gate insulating film, semiconductor layer and source-drain electrode, and
Form the operation of channel region.
4. according to the manufacturing approach of each described semiconductor element substrate in the claim 1 ~ 3, wherein, said organic material is the resin combination that contains resin.
5. according to the manufacturing approach of each described semiconductor element substrate in the claim 1 ~ 4, wherein, the processing time of said Cement Composite Treated by Plasma is 1 ~ 10 minute.
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