KR20100099118A - Polyester resin solution for production of thermally cured film - Google Patents

Abstract

(식 중, A, B는 환구조를 포함하는 유기기를 나타낸다.)After cured film formation, it provides high solvent resistance, liquid crystal orientation, high transparency and high leveling property, and when cured film is formed, it is to provide a material that can be dissolved in a glycol-based solvent applicable to the flattening film production line of color filters. .
The polyester resin solution for thermosetting film formation containing the polyester polymer containing the structural unit represented by following formula (1), the cured film obtained by these, a liquid crystal aligning layer, and a planarization film.
[Formula 1]

(In formula, A and B represent the organic group containing ring structure.)

Description

Polyester resin solution for thermosetting film formation {POLYESTER RESIN SOLUTION FOR PRODUCTION OF THERMALLY CURED FILM}

The present invention relates to a polyester resin solution for forming a thermosetting film and a cured film obtained therefrom. More specifically, it relates to the application of the polyester resin solution for thermosetting film formation, its cured film, and this cured film which have high transparency and flatness, and has liquid crystal aligning ability. This thermosetting film formation resin solution is especially suitable as a color filter overcoat agent having a liquid crystal alignment function in a liquid crystal display.

Generally, in optical devices such as liquid crystal display devices, organic electroluminescent (EL) devices, and solid state imaging devices, a protective film is provided to prevent the surface of the device from being exposed to solvents or heat during the manufacturing process. Such a protective film has high adhesion to the substrate to be protected, high solvent resistance, and also requires performance such as transparency and heat resistance.

When such a protective film is used as a protective film for a color filter used in a color liquid crystal display device or a solid-state image pickup device, the protective film generally has the capability of flattening the color filter or the black matrix resin of the base substrate, that is, as a flattening film. Required. In particular, when manufacturing a color liquid crystal display device of the STN method or the TFT method, it is necessary to perform a very precise bonding accuracy between the color filter substrate and the counter substrate, and it is necessary to make the cell gap between the substrates uniform. In addition, in order to maintain the transmittance of light passing through the color filter, these planarization films, which are their protective films, require high transparency.

On the other hand, low cost reduction and weight reduction have been recently investigated by introducing a retardation material into a cell of a liquid crystal display, and a material obtained by applying and orienting a liquid crystal monomer and orienting such a retardation material is generally used. In order to orient this retardation material, the underlayer film needs to be a material having orientation after rubbing treatment. For this reason, after forming a liquid crystal aligning film on the overcoat of a color filter, a phase difference material is formed (refer FIG. 2 (a)). If a film having a liquid crystal alignment film and an overcoat of a color filter (see Fig. 2 (b)) can be formed, such a material is strongly demanded since it is possible to obtain great advantages such as low cost and a reduction in the number of processes.

Generally, high transparency acrylic resin is used for the overcoat of this color filter. Glycol solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, and ester solvents such as ethyl lactate and butyl lactate are widely used in these acrylic resins from the viewpoint of safety and handling properties. Such acrylic resins have given heat resistance and solvent resistance by thermal curing or photocuring (Patent Documents 1 and 2). However, the conventional thermosetting and photocurable acrylic resins exhibit proper transparency and flattening properties, but rubbing treatment of such flattening films does not show sufficient orientation.

On the other hand, the material which consists of solvent-soluble polyimide and a polyamic acid is used normally for a liquid crystal aligning film. It is reported that these materials impart solvent resistance by completely imidating during post-baking and exhibit sufficient orientation by rubbing treatment (Patent Document 3). However, in the case of the flattening film of the color filter, there was a problem such that the flatness and transparency greatly decreased. In addition, polyimide and polyamic acid are dissolved in a solvent such as N-methylpyrrolidone or γ-butyrolactone, but have low solubility in a solvent of a glycol solvent or an ester solvent and have difficulty in application to a flattening film production line.

Japanese Patent Application Laid-Open No. 2000-103937 Japanese Patent Application Laid-Open No. 2000-119472 Japanese Patent Laid-Open No. 2005-037920

The present invention has been made on the basis of the above circumstances, and the problem to be solved is high solvent resistance, liquid crystal orientation, high transparency and high flattening property after cured film formation, and also applied in the production line of flattening film of color filter when cured film is formed. The present invention provides a material that can be dissolved in a possible glycol solvent or a lactic ester solvent.

MEANS TO SOLVE THE PROBLEM This inventor discovered this invention as a result of earnestly researching in order to solve the said subject. That is, the polyester resin solution for thermosetting film formation containing the polyester polymer containing the structural unit represented by following formula (1) as a 1st viewpoint.

(In formula, A is at least 1 sort (s) chosen from the group which consists of group represented by following formula (A-1)-formula (A-14), B is a following formula (B-1)-a formula (B-5) It is at least one kind selected from the group consisting of appearing groups.)

The polyester polymer containing the structural unit represented by said Formula (1) by a 2nd viewpoint to the polyester polymer obtained by making the tetracarboxylic dianhydride represented by following formula (i) react with the diol compound represented by following formula (ii). The polyester resin solution for thermosetting film formation as described in the 1st viewpoint which is a polyester polymer obtained by making glycidyl methacrylate react further.

(In formula, A and B are the same as the definition in said Formula (1).)

The polyester resin solution for thermosetting film formation as described in the 1st viewpoint or 2nd viewpoint that the weight average molecular weight of the polyester polymer containing the structural unit represented by said Formula (1) as a 3rd viewpoint is 1,000-30,000 in polystyrene conversion.

The polyester resin solution for thermosetting film formation as described in a 2nd viewpoint or a 3rd viewpoint whose substitution rate by a glycidyl methacrylate group in the carboxyl group in the said polyester polymer is 4 to 70 by a 4th viewpoint.

The cured film obtained using the polyester resin solution for thermosetting film formation in any one of a 1st viewpoint thru | or a 4th viewpoint as a 5th viewpoint.

The liquid crystal aligning layer obtained using the polyester resin solution for thermosetting film formation in any one of a 1st viewpoint thru | or a 4th viewpoint as a 6th viewpoint.

The flattening film obtained using the polyester resin solution for thermosetting film formation in any one of a 1st viewpoint thru | or a 4th viewpoint as a 7th viewpoint.

Since the polyester resin solution for thermosetting film formation of this invention can form the cured film which has liquid crystal aligning ability in addition to high planarization property, high transparency, and high solvent tolerance, it can be used as a formation material of a liquid crystal aligning film or a planarization film. In particular, it is possible to form the overcoat layer of the liquid crystal aligning film and the color filter which were conventionally formed independently at once with a "liquid crystal aligning layer" having both characteristics, thereby simplifying the manufacturing process and reducing the cost by reducing the number of processes. Can be realized.

Moreover, since the polyester resin solution for thermosetting film formation of this invention is melt | dissolved in the glycol solvent and the lactic acid ester solvent, it can be used suitably for the production line of the planarization film which mainly uses these solvents.

1 is a schematic diagram showing a cured film formed when a thermosetting polyester resin solution is applied to a stepped substrate.
FIG. 2: is a schematic diagram contrasting the liquid crystal aligning layer (a) by the prior art, and the liquid crystal aligning layer (b) using the polyester resin solution for thermosetting film formation of this invention.

As described above, in the conventionally proposed cured films of acrylic resins and polyimide resins, none of the performances such as flatness, transparency, and orientation required for the liquid crystal alignment film and the planarization film is sufficiently satisfied.

Although there have been some proposals for the use of polyester resins as alignment materials for liquid crystal display devices (see Japanese Patent Application Laid-Open Nos. 5-158055 and 2002-229039), all of them do not have thermosetting properties. Was deteriorated.

This invention is characterized by the point which aimed at the above-mentioned performance improvement using the thermosetting polyester resin solution, ie, it is the polyester resin solution for thermosetting film formation containing the polyester polymer shown below. It will be described in detail below.

<Polyester Polymer>

The polyester polymer used for this invention is a polyester polymer (henceforth a polyester polymer of Formula (1)) containing the structural unit represented by following formula (1).

In said Formula (1), A is at least 1 sort (s) chosen from the group which consists of group represented by following formula (A-1)-formula (A-14), B is following formula (B-1)-formula (B-5) It is at least one kind selected from the group consisting of groups represented by).

Among the groups represented by the above formulas (A-1) to (A-14), a group particularly selected from formulas (A-1) to (A-4) and (A-8) is preferable.

Moreover, it is especially preferable that it is group chosen from (B-1)-(B-4) among the group represented by said formula (B-1)-formula (B-5).

One type or two types of A and B of Formula (1) contained in a polyester polymer may respectively be independent. It is preferable that this polyester polymer is a polymer containing the structural unit represented by Formula (1) and the structural unit represented by following formula (iii). More preferably, it is a polyester polymer which consists of a structural unit represented by Formula (1) and a structural unit represented by Formula (iii).

(In said formula, A and B are the same as the definition in Formula (1).)

The weight average molecular weight of the polyester polymer of the formula (1) is 1,000 to 30,000, preferably 1,500 to 10,000. When the weight average molecular weight of the polyester polymer of Formula (1) is smaller than the said range, orientation and solvent resistance may fall, and when it exceeds the said range, planarization property may fall.

<Method for Producing Polyester Polymer of Formula (1)>

The polyester polymer of formula (1) used in the present invention is produced after reacting a tetracarboxylic dianhydride (acid component) represented by the following formula (i) with a diol compound (diol component) represented by the following formula (ii): It can obtain by adding glycidyl methacrylate to a part of carboxyl group.

In said formula, A and B are the same as the definition in said Formula (1).

Specifically, by reacting the formula (i) with the formula (ii) to form a polymer (hereinafter also referred to as a specific polymer) consisting of a structural unit represented by the following formula (iii) and glycidyl meta to a part of the carboxyl group of the polymer It can be obtained by adding acrylate.

In said formula, A and B are the same as the definition in said Formula (1).

<Production of Polyester Polymer Composed of Structural Unit Represented by Formula (iii)>

The blending ratio of the total amount (the total amount of the acid component) and the total amount (the total amount of the diol component) of the tetracarboxylic dianhydride and the diol compound in the polyester polymer (hereinafter referred to as a specific polymer) composed of the structural unit represented by the formula (iii), ie It is preferable that <total number-of-moles of diol compound> / <total number-of-moles of tetracarboxylic dianhydride compound> is 0.5-1.5. As in the conventional polycondensation reaction, the closer the molar ratio is to 1, the higher the degree of polymerization of the specific polymer produced and the higher the molecular weight. In addition, the terminal of a specific polymer depends on the compounding ratio of a positive component, and when an acid component is excessively reacted, the terminal becomes an acid anhydride easily.

The terminal of the specific polymer is preferably protected with dicarboxylic anhydride or alcohol in order to avoid deterioration in storage stability. It is more preferable to protect with acid anhydride from the point of orientation.

The terminal of the said specific polymer changes with the compounding ratio of an acid component and a diol component. For example, when the acid component is excessively reacted, the terminal tends to be an acid anhydride.

Moreover, when superposing | polymerizing using an excess diol component, a terminal becomes a hydroxyl group easily. In this case, the terminal hydroxyl group can be reacted with carboxylic anhydride to seal the terminal hydroxyl group with an acid anhydride. Examples of such carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, tetrahydrophthalic acid Anhydride, methyltetrahydrophthalic anhydride, bicyclo [2.2.2] octene-2,3-dicarboxylic acid anhydride, and the like.

The reaction temperature between the acid component and the diol component in the preparation of the specific polymer may be selected at any temperature of 50 to 200 ° C, preferably 80 to 170 ° C. For example, the reaction temperature is 100 ℃ to 140 ℃, reaction time 2 to 48 hours can be obtained a specific polymer.

In addition, the reaction temperature in the case of protecting a terminal hydroxyl group with an acid anhydride can select arbitrary temperature of 50-200 degreeC, Preferably it is 80-170 degreeC.

The reaction between the acid component and the diol component is usually carried out in a solvent. The solvent which can be used at this time will not be specifically limited if it does not contain the functional group which reacts with acid anhydrides, such as a hydroxyl group and an amino group. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, dimethyl sulfone , Hexamethyl sulfoxide, m-cresol, γ-butyrolactone, cyclohexanone, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate And methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate and the like.

Although these solvents may be used independently or may be used in mixture, propylene glycol monomethyl ether acetate is more preferable from a safety point and the applicability to the line of the overcoat agent of a color filter.

Moreover, even if the solvent does not melt | dissolve a specific polymer, you may mix and use it with the said solvent in the range which does not precipitate the specific polymer produced | generated by the polymerization reaction.

It is also possible to use catalysts in the preparation of certain polymers.

Specific examples of the catalyst used in the polymerization of a specific polymer include benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltripropylammonium chloride, benzyltripropylammonium bromide, benzyltrimethyl Phosphonium chloride, benzyl trimethyl phosphonium bromide, benzyl triethyl phosphonium chloride, benzyl triethyl phosphonium bromide, benzyl tripropyl phosphonium chloride, benzyl tripropyl phosphonium bromide, tetraphenyl phosphonium chloride, tetraphenyl phosphonium bromide, etc. Quaternary ammonium salts may be mentioned.

The solution containing the specific polymer obtained in this way can then be used for reaction with glycidyl methacrylate. In addition, after precipitating and recovering in poor solvents such as water, methanol, ethanol, diethyl ether and hexane, the solution redissolved in the solvent may be used for reaction with glycidyl methacrylate.

<Addition of glycidyl methacrylate>

The polyester polymer of Formula (1) used for this invention can be obtained by adding glycidyl methacrylate to the specific polymer represented by Formula (iii) obtained by the above method.

Specific examples of the method for adding glycidyl methacrylate to the specific polymer, for example, by adding glycidyl methacrylate to the polymerization solution of the specific polymer and further adding a polymerization inhibitor 60 to 150 The polyester polymer of the said Formula (1) can be obtained by making it react by C and reaction time for 3 to 48 hours.

Examples of the polymerization inhibitor include 2,6-diisobutylphenol, 3,5-di-t-butylphenol, 3,5-di-t-butylcresol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, t -Butyl catechol, etc. are mentioned.

In the polyester polymer of formula (1) used in the present invention, the carboxyl group in the specific polymer represented by formula (iii) is glycidyl at a ratio of 5 to 70%, preferably 10 to 60%, relative to the total carboxyl equivalent. It is preferable that it is substituted by methacrylate.

When the substitution rate of glycidyl methacrylate is smaller than the said numerical range, the hardening degree of a cured film will weaken and solvent tolerance may fall. On the contrary, when it exceeds the said numerical range, application | coating of the retardation material used for the layer (layer formed on it after liquid crystal aligning layer formation) mentioned later may become difficult.

<Solvent>

The polyester resin solution for thermosetting film formation of this invention is used in the solution state melt | dissolved in the solvent in many cases. The solvent used at this time will melt | dissolve a polyester polymer and the other additives mentioned later as needed, and if the solvent which has such a dissolving power, the kind, structure, etc. will not be restrict | limited in particular.

As such a solvent, the solvent used for superposition | polymerization of a polyester polymer, and the following solvent are mentioned. For example, methyl cellosolve acetate, ethyl cellosolve acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol propyl ether, ethyl lactate, butyl lactate, cyclohexa Knoll, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, etc. are mentioned.

These solvents can be used individually by 1 type or in combination of 2 or more types.

<Other additives>

Further, the polyester resin solution for forming a thermosetting film of the present invention, as long as the effect of the present invention is not impaired, adhesion aids such as radical generators such as peroxides, surfactants, rheology regulators, and silane coupling agents, Pigments, dyes, storage stabilizers, antifoaming agents or dissolution accelerators such as polyhydric phenols and polycarboxylic acids.

<Polyester Resin Solution for Thermosetting Film Formation>

The resin solution for thermosetting film formation of this invention is a solution which the polyester polymer containing the structural unit represented by said Formula (1) melt | dissolved in the solvent, and may further contain one or more types of other additives as needed. Solution.

Among these, the preferable example of the polyester resin solution for thermosetting film formation of this invention is as follows.

[1]: Polyester resin solution for thermosetting film formation in which polyester polymer is dissolved in solvent.

[2]: Polyester resin solution for thermosetting film formation in which one kind of polyester polymer and other additives are dissolved in a solvent.

The ratio of solid content in the polyester resin solution for thermosetting film formation of this invention is not specifically limited as long as each component is melt | dissolving uniformly in a solvent, It is 1-80 mass%, Preferably it is 5-60 mass%. More preferably, it is 10-50 mass%. Solid content means here the thing remove | excluding the solvent from the all components of the polyester resin solution for thermosetting film formation.

In preparation of the polyester resin solution for thermosetting film formation of this invention, the solution of the polyester polymer obtained by the polymerization reaction in a solvent can be used as it is.

Moreover, you may add an additional solvent for the purpose of concentration adjustment. At this time, the solvent used for preparation of a polyester polymer and the solvent used for concentration adjustment at the time of preparation of the polyester resin solution for thermosetting film formation may be same or different.

Moreover, it is preferable to use the prepared solution of the polyester resin solution for thermosetting film formation after filtering using a filter etc. of about 0.2 micrometer in diameter.

<Film, Cured Film, Liquid Crystal Alignment Layer, and Flattening Film>

The polyester resin solution for forming a thermosetting film of the present invention may be a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a metal, for example, a substrate coated with aluminum, molybdenum, chromium, glass substrate, Rotary coating, shedding, roll coating, slit coating, slit followed by rotary coating on quartz substrate, ITO substrate, etc.) or film (for example, resin film such as triacetyl cellulose film, polyester film, acrylic film, etc.) After coating by inkjet coating, printing, or the like, the coating film can be formed by pre-drying (prebaking) with a hot plate or an oven. Thereafter, a coating is formed by heat treatment of the coating film.

As conditions of this heat processing, the heating temperature and heating time suitably selected from the range of the temperature of 70 degreeC-160 degreeC, and the time of 0.3 to 60 minutes are employ | adopted, for example. The heating temperature and the heating time are preferably 80 ° C to 140 ° C and 0.5 to 10 minutes.

In addition, the film thickness of the film formed from the polyester resin solution for thermosetting film formation is 0.1-30 micrometers, for example, and can select suitably in consideration of the level | step difference of the board | substrate to be used, and optical and electrical property.

The postbaking is generally carried out at a heating temperature selected in the range of 140 ° C. to 250 ° C. for 5 to 30 minutes on a hot plate and 30 to 90 minutes in an oven.

By curing the film obtained from the polyester resin solution for forming a thermosetting film of the present invention under the above conditions, it is possible to sufficiently planarize the steps of the substrate and to form a cured film and a flattening film having high transparency.

The cured film formed by such a method can be made to function as a layer which orientates a liquid crystal material orientation layer, ie, a compound which has liquid crystallinity, by performing a rubbing process.

As a condition of the rubbing treatment, generally, conditions such as a rotational speed of 300 to 1000 rpm, a feeding speed of 3 to 20 mm / sec, and an indentation amount of 0.1 to 1 mm are used.

Thereafter, residue generated by rubbing is removed by ultrasonic cleaning using pure water or the like.

After retardation material is apply | coated on the liquid crystal aligning layer formed by such a method, the layer which has optical anisotropy can be formed by photocuring a retardation material in a liquid crystal state.

As a retardation material, the liquid crystal monomer which has a polymeric group, the composition containing this, etc. are used, for example.

Moreover, when the base material which forms a liquid crystal aligning layer is a film, it is useful as an optically anisotropic film.

Further, after bonding two substrates having the liquid crystal alignment layer formed by the above method so that the liquid crystal alignment layers face each other, a liquid crystal may be injected between these substrates to form a liquid crystal display device in which the liquid crystal is aligned.

For this reason, the polyester resin solution for thermosetting film formation of this invention can be used suitably for various optically anisotropic films and liquid crystal display elements.

In addition, the polyester resin solution for forming a thermosetting film of the present invention has a high flattening property, so that cured films such as protective films, planarizing films, and insulating films in various displays such as thin film transistor (TFT) type liquid crystal display devices and organic EL devices can be used. It is also useful as a material to be formed, and is particularly suitable as a material for forming an overcoat material of a color filter, an interlayer insulating film of a TFT type liquid crystal element, an insulating film of an organic EL element, and the like.

[Example]

Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.

[Weak symbol used in the Example]

The meaning of the abbreviation used in the following Examples is as follows.

<Polyester Polymer Raw Material>

BPDA: biphenyltetracarboxylic dianhydride

6FDA: 4,4 '-(hexafluoroisopropylidene) phthalic dianhydride

HBPA: hydrogenated bisphenol A

HBPDA: hydrogenated biphenyltetracarboxylic dianhydride

CHDO: 1,4-cyclohexanediol

GMA: glycidyl methacrylate

THPA: 1,2,5,6-tetrahydroxyphthalic anhydride

BTEAC: benzyltriethylammonium chloride

TPPB: tetraphenylphosphonium bromide

TBC: 3,5-di-t-butylcresol

<Polyimide precursor raw material>

CBDA: cyclohexanetetracarboxylic dianhydride

pDA: p-phenylenediamine

<Acrylic Polymer Raw Material>

MAA: methacrylic acid

MMA: Methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

CHMI: N-cyclohexylmaleimide

AIBN: azobisisobutyronitrile

<Epoxy compound>

CEL: CELLOXIDE P-2021 (product name) (compound name: 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate) made by Daicel Chemical Industries Limited.

<Solvent>

PGMEA: Propylene glycol monomethyl ether acetate

NMP: N-methylpyrrolidone

The number average molecular weight and weight average molecular weight of the polyester polymer, the polyimide precursor, and the acrylic copolymer obtained according to the synthesis examples described below were obtained by using the GPC apparatus (Shodex® columns KF803L and KF804L) manufactured by JASCO Corporation. Hydrofuran was measured under the condition that the flow rate was eluted in a column (column temperature of 40 ° C) at a flow rate of 1 ml / min. In addition, the following number average molecular weight (henceforth Mn.) And weight average molecular weight (henceforth Mw.) Were shown by polystyrene conversion value.

Synthesis Example 1

BPDA 40.0g, HBPA 35.3g and BTEAC 0.77g were reacted in PGMEA 175.7g at 120 ° C for 1 hour, then TH315.315g was added and reacted for 19 hours to obtain a solution of a specific polymer (solid content concentration: 30.0% by mass) (P1 ). Mn of the obtained specific polymer was 1,100 and Mw was 2,580.

Synthesis Example 2

Polyester polymer solution (solid content concentration: 30.0 mass%) was obtained by adding 8.19g of GMA, 8.9mg of TBC, and 19.1g of PGMEA to 50g of solution (P1) of the specific polymer obtained by the synthesis example 1, and reacting at 100 degreeC for 9 hours. P2). Mn of the obtained polyester polymer was 3,040 and Mw was 7,290.

&Lt; Synthesis Example 3 &

Polyester polymer solution (solid content concentration: 30.0 mass%) was obtained by adding 4.91 g of GMA, 5.3 mg of TBC, and 11.5 g of PGMEA to 50 g of solution (P1) of the specific polymer obtained by the synthesis example 1, and reacting at 100 degreeC for 9 hours. P3). Mn of the obtained polyester polymer was 2,820 and Mw was 6,200.

&Lt; Synthesis Example 4 &

Polyester polymer solution (solid content concentration: 30.0 mass%) was obtained by adding 2.46 g of GMA, 2.7 mg of TBC, and 11.5 g of PGMEA to 50 g of solution (P1) of the specific polymer obtained by the synthesis example 1, and reacting at 100 degreeC for 9 hours. P4). Mn of the obtained polyester polymer was 1,470 and Mw was 4,970.

&Lt; Synthesis Example 5 &

6FDA 4 0.0g, CHDO 11.3g, and BTEAC 0.51g were reacted in PGMEA 119.7g at 120 ° C for 1 hour, and then reacted for 19 hours with 2.195g of THPA to obtain a solution of a specific polymer (solid concentration: 30.0% by mass) ( P5). Mn of the obtained specific polymer was 2,100 and Mw was 3,800.

&Lt; Synthesis Example 6 &

Polyester polymer solution (solid content: 30.0 mass%) was obtained by adding 2.63 g of GMA, 2.8 mg of TBC, and 6.13 g of PGMEA to 65.0 g of the solution (P5) of the specific polymer obtained by the synthesis example 5, and reacting at 100 degreeC for 9 hours. (P6). Mn of the obtained polyester polymer was 3,790 and Mw was 8,340.

Synthesis Example 7

The solution (solid content concentration: 30.0 mass%) of the specific polymer was obtained by making 20.0 g of HBPDA, 20.3 g of HBPA, 0.14 g of TPPB, and 4.67 g of THPA react for 19 hours at a temperature of 120 ° C. in 105.1 g of PGMEA (P7). Mn of the obtained specific polymer was 1,600 and Mw was 2,800.

Synthesis Example 8

A polyester polymer solution (solid content: 30.0 mass%) was obtained by adding 4.13 g of GMA, 1 mg of TBC, and 7.03 g of PGMEA to 45 g of the solution (P7) of the specific polymer obtained in the synthesis example 7, and reacting at 100 degreeC for 9 hours. P8). Mn of the obtained polyester polymer was 1,900 and Mw was 4,200.

Synthesis Example 9

The polyimide precursor solution (solid content concentration: 30.0 mass%) was obtained by making CBDA17.7g and pDA10.2g react in NMP66.4g for 24 hours at 23 degreeC (P9). Mn of the obtained polyimide precursor was 5,800 and Mw was 12,500.

Synthesis Example 10

Solution of the acrylic copolymer by using 10.9 g of MAA, 35.3 g of CHMI, 25.5 g of HEMA, 28.3 g of MMA as the monomer component, and 5 g of AIBN as the radical polymerization initiator, and polymerizing them in 150 g of solvent PGMEA at a temperature of 60 ° C. to 100 ° C. (Solid content concentration: 40.0 mass%) was obtained (P10). Mn of the obtained acrylic copolymer was 3,800 and Mw was 6,700.

<Examples 1 to 5 and Comparative Examples 1 to 3>

Each composition of Examples 1-5 and Comparative Examples 1-3 was prepared with the composition shown in Table 1, and planarization, solvent tolerance, transmittance | permeability, and orientation property were evaluated about each.

Polyester Polymer *
Solution (g) Other ingredients (g) Solvent (g) Example 1 P2
20 PGMEA
2.22 Example 2 P3
20 PGMEA
2.22 Example 3 P4
20 PGMEA
2.22 Example 4 P6
20 PGMEA
2.22 Example 5 P8
20 PGMEA
2.22 Comparative Example 1 P1
20 PGMEA
2.22 Comparative Example 2 P9
20 NMP
2.22 Comparative Example 3 P10
20 CEL
1.2 PGMEA
2.80

* P1: specific polymer solution P2 ~ P4, P6, P8: polyester polymer solution

P9: polyimide precursor solution P10: acrylic polymer solution

[Evaluation of Flatness]

Each resin solution of Examples 1 to 5 and Comparative Examples 1 to 3 was coated on a stepped substrate (made of glass) with a height of 0.5 μm, a line width of 10 μm, and a space of 50 μm between lines using a spin coater. And prebaked at a temperature of 100 ° C. for 120 seconds on a hot plate to form a coating film having a film thickness of 2.8 μm. The film thickness was measured using F20 by FILMETRICS. This coating film was heated at the temperature of 230 degreeC for 30 minutes, post-baking was carried out, and the cured film with a film thickness of 2.5 micrometers was formed.

The film thickness difference between the coating film on the stepped substrate line and the coating film on the space was measured (see FIG. 1), and the flattening ratio (DOP) = 100 x [1- {film thickness difference (µm) of the film / step height (0.5µm )}] Was used to determine the planarization rate.

[Evaluation of Solvent Tolerance]

Each resin solution of Examples 1 to 5 and Comparative Examples 1 to 3 was applied to a silicon wafer using a spin coater, and then prebaked at a temperature of 100 ° C. for 120 seconds on a hot plate for a film thickness of 2.8 μm. Formed. The film thickness was measured using F20 by FILMETRICS. This coating film was post-baked on the hotplate for 30 minutes at the temperature of 230 degreeC, and the cured film with a film thickness of 2.5 micrometers was formed.

After immersing this cured film in PGMEA or NMP for 60 second, it dried at the temperature of 100 degreeC for 60 second, respectively, and measured the film thickness. (Circle) and the thing which reduced the film thickness after immersion were made into X that there was no change in the film thickness after PGMEA or NMP immersion.

[Evaluation of Light Transmittance (Transparency)]

Each resin solution of Examples 1 to 5 and Comparative Examples 1 to 3 was coated on a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2.8 μm. A coating film was formed. The film thickness was measured using F20 by FILMETRICS. This coating film was post-baked on the hotplate for 30 minutes at the temperature of 230 degreeC, and the cured film was formed.

The transmittance | permeability at the wavelength of 400 nm was measured for this cured film using the ultraviolet visible spectrophotometer (Shimadzu Corporation SHIMADSUUV-2550 model number).

[Evaluation of Orientation]

Each resin solution of Examples 1 to 5 and Comparative Examples 1 to 3 was applied onto an ITO substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2.8 μm. A coating film was formed. The film thickness was measured using F20 by FILMETRICS. This film was post-baked on the hotplate for 30 minutes at the temperature of 230 degreeC, and the cured film was formed.

This cured film was rubbed at a rotational speed of 700 rpm, a feed rate of 10 mm / sec, and an indentation amount of 0.45 mm. The rubbed substrate was ultrasonically cleaned for 5 minutes with pure water. After apply | coating the phase difference material which consists of liquid crystal monomers on this board | substrate using a spin coater, it prebaked on the hotplate for 40 second at 100 degreeC, and 30 second at 55 degreeC, and formed the coating film of 1.1 micrometers in thickness. The substrate was exposed to 2,000 mJ under a nitrogen atmosphere. The produced board | substrate was interposed in the polarizing plate, and the orientation was visually confirmed. When the board | substrate was inclined at 45 degree | times, and when it did not incline, the thing which markedly changed the light transmittance (circle) and the thing which did not change were made into X.

[Evaluation results]

The results of the above evaluation are shown in Table 2 below.

Planarization rate (%)
Solvent resistance Orientation
Transmittance (%)
PGMEA NMP Example 1 90 ○ ○ ○ 96 Example 2 85 ○ ○ ○ 97 Example 3 80 ○ ○ ○ 97 Example 4 87 ○ ○ ○ 98 Example 5 88 ○ ○ ○ 98 Comparative Example 1 - X X - - Comparative Example 2 25 ○ ○ ○ 85 Comparative Example 3 88 ○ ○ X 96

Examples 1 to 5 had a high planarization rate and were also resistant to both PGMEA and NMP. Both exhibited good orientation and achieved high transmittance (transparency) even after high temperature firing.

On the other hand, in the comparative example 1, the cured film was not formed.

In addition, Comparative Example 2 had good solvent resistance and orientation, but had a very low planarization rate.

In addition, Comparative Example 3 had good planarization rate, solvent resistance, and transmittance, but deteriorated orientation.

As described above, the polyester resin solution for forming a thermosetting film of the present invention can use a glycol solvent such as propylene glycol monomethyl ether acetate when forming a cured film, and the obtained cured film has excellent light transmittance, solvent resistance, and flatness. All performances of chemical conversion and orientation were good.

[Industrial Availability]

The polyester resin solution for forming a thermosetting film according to the present invention is very useful as a liquid crystal alignment layer of an optically anisotropic film or a liquid crystal display device, and also a protective film in various displays such as a thin film transistor (TFT) type liquid crystal display device and an organic EL device. And a material for forming a cured film such as a flattening film or an insulating film, in particular, an interlayer insulating film of a TFT type liquid crystal element, a protective film of a color filter, an insulating film of an organic EL element, or the like.

Claims (7)

The polyester resin solution for thermosetting film formation containing the polyester polymer containing the structural unit represented by following formula (1).
[Formula 1]

(In formula, A is at least 1 sort (s) chosen from the group which consists of group represented by following formula (A-1)-formula (A-14), B is a following formula (B-1)-a formula (B-5) It is at least one kind selected from the group consisting of appearing groups.)
(2)

(3)

[Chemical Formula 4]

The method of claim 1,
Glyciy is further added to the polyester polymer obtained by making the polyester polymer containing the structural unit represented by said Formula (1) react with the tetracarboxylic dianhydride represented by following formula (i), and the diol compound represented by following formula (ii). The polyester resin solution for thermosetting film formation which is a polyester polymer obtained by making dimethyl methacrylate react.
[Chemical Formula 5]

(In formula, A and B are the same as the definition in said Formula (1).)
3. The method according to claim 1 or 2,
The polyester resin solution for thermosetting film formation whose weight average molecular weights of the polyester polymer containing the structural unit represented by said Formula (1) are 1,000-30,000 in polystyrene conversion.
4. The method according to claim 2 or 3,
The polyester resin solution for thermosetting film formation whose substitution rate by glycidyl methacrylate in a carboxyl group in the said polyester polymer is 5 to 70%.
The cured film obtained using the polyester resin solution for thermosetting film formation in any one of Claims 1-4.
The liquid crystal aligning layer obtained using the polyester resin solution for thermosetting film formation in any one of Claims 1-4.
The planarization film obtained using the polyester resin solution for thermosetting film formation in any one of Claims 1-4.

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