KR20070013209A - Positive type photosensitive resin composition and cured film manufactured therefrom - Google Patents

Abstract

A positive type of photosensitive resin composition for fabricating cured film is provided to exhibit high transmission even when the composition is treated under hot calcination and by a resist stripping solution by comprising a compound having vinyl ether group and another compound having block isocyanate group, as well as alkaline soluble resin, photoacid generator and solvent. The composition includes: (A) alkaline soluble resin having number average molecular weight of 2,000 to 30,000; (B) a compound having at least two vinyl ether groups in a molecule; (C) another compound having at least two block isocyanate groups in a molecule; (D) photoacid generator; and (E) solvent. The alkaline soluble resin comprises a functional group to conduct hot cross-linking reaction with the compound(B) and another functional group to conduct heat curing reaction with the compound(C).

Description

Positive type photosensitive resin composition and cured film obtained therefrom {Positive Type Photosensitive Resin Composition And Cured Film Manufactured Therefrom}

1 is a diagram showing a film thickness (μm, the film thickness remaining after melting in an exposed portion) with respect to an irradiation dose (mJ / cm ² ).

This invention relates to a positive photosensitive resin composition, its manufacturing method, the pattern formation method using this resin composition, and the cured film obtained from this resin composition. In more detail, this invention is a positive-type photosensitive resin composition suitable for use of a display material, its manufacturing method, the pattern formation method using this resin composition, the cured film obtained from this resin composition, and various using this cured film. It is about the material.

In general, in display elements such as thin film transistor (TFT) type liquid crystal display elements and organic electroluminescent (EL) elements, patterned electrode protective films, planarization films, insulating films and the like are provided. As a material which forms these films | membrane, the photosensitive resin composition which has the characteristic of having sufficient flatness while having a small number of processes for obtaining the required pattern shape among the photosensitive resin compositions is used more widely than before.

And these films mentioned above have excellent process resistance, such as heat resistance, solvent resistance, and long-term plastic resistance, good adhesion to the lower substrate, and wide process margins capable of forming patterns under various process conditions according to the intended use. It is required to have a variety of properties such as to have, moreover, high sensitivity and high transparency, and less film bleeding after development. Here, conventionally, such a photosensitive resin composition has been a resin containing a naphthoquinone diazido compound.

By the way, sensitivity is mentioned as an important characteristic among the required characteristics of such a photosensitive resin material. Since the improvement of the sensitivity enables a significant reduction of the production time in the industrial production of display elements and the like, in the present situation where the demand for liquid crystal displays is significantly increasing, the sensitivity is required for this kind of photosensitive resin material. Being one of the most important characteristics.

However, the conventional photosensitive resin material containing the above-mentioned naphthoquinone diazido compound was not fully satisfying in terms of sensitivity. Although it is also possible to improve the sensitivity by increasing the solubility in the alkaline developer with respect to the polymer in the material, there is a limit to this method, and the solubility of the unexposed part also occurs, and the residual film ratio is increased. There existed a fault which falls and this becomes a cause of film | membrane spreading in the board | substrate for large displays.

Therefore, until now, various patent applications have been applied for the purpose of high sensitivity of the photosensitive resin material. For example, the radiation sensitive resin composition containing at least some alkali-soluble resin, a specific polyhydroxy compound, and its derivative (s) is proposed (for example, refer patent document 1). However, this proposed material had problems with storage stability and the like because of its high symmetry.

Moreover, the positive photosensitive resin composition containing the alkali-soluble phenol resin and the positive radiation sensitive resin composition containing a radiation sensitive compound (for example, refer patent document 2), and the specific alkali-soluble resin and quinonediazido compound. (For example, refer patent document 3). However, these have a problem in transparency and stability at the time of baking for the time since novolak resin is used for a binder polymer.

As mentioned above, it is very difficult to develop the photosensitive resin composition which satisfy | fills other characteristics also and has a desired level of high sensitivity, and it was difficult to obtain satisfactory photosensitive resin composition by the simple combination of the prior art.

In general, as a conventional photosensitive resin material containing a naphthoquinone diazido compound, photo-bleaching is performed to prevent coloring of the cured film by the naphthoquinone diazido compound and deterioration of transparency after exposure development. However, even if this photo-bleaching process is carried out, the obtained film is colored when the resulting film is baked at a high temperature of about 250 ° C., and the color is decreased, and even when it is baked at a temperature lower than this, for example, at 230 ° C. for a long time, the light transmittance is decreased. (Coloring) appears, and furthermore, even a chemical treatment such as an amine solution, which is a resist stripping liquid, causes a problem that the light transmittance is lowered and the transparency is deteriorated. Thus, a conventional photosensitive resin material containing a naphthoquinone diazido compound Has a problem in terms of such heat resistance and chemical resistance (see Patent Document 4, for example).

On the other hand, chemically amplified resists have been developed as a photosensitive material having high sensitivity and high resolution. Conventional chemically amplified resists developed as resists for semiconductors can be adapted to light sources (KrF, ArF) that are shorter in wavelength than i-rays, and can form finer patterns. In the presence of the liquid, the bonding portion of the protecting group and the thermal crosslinking portion of the ether bond are easily decomposed, the heat resistance and chemical resistance are remarkably low, and it is almost impossible to use it as a permanent membrane (see Patent Document 5, for example). In addition, in order to enable thermal curing, even when a crosslinking system of epoxy or aminoplasts is introduced into a chemically amplified resist, the exposed portion is exposed to the effect of acid generated in the photoacid generator (PAG) in the resist by exposure. Since crosslinking advances and the problem of dissolution contrast with an unexposed part arises newly, it is difficult to introduce | transduce such crosslinking system into the chemically amplified resist.

[Patent Document 1] Japanese Patent Application Laid-Open No. 4-211255

[Patent Document 2] Japanese Patent Application Laid-Open No. 9-006000

[Patent Document 3] Japanese Patent Application Laid-Open No. 8-044053

[Patent Document 4] Japanese Patent Application Laid-Open No. 4-352101

[Patent Document 5] US Patent No. 5075199

The present invention has been made in view of the above circumstances, and the problem to be solved is sufficiently high sensitivity and no film reduction of unexposed portions during development, and also maintains high transmittance even when baked under high temperature after film formation. To provide a positive photosensitive resin composition which does not cause a decrease in film thickness and a decrease in transmittance even when exposed to a resist stripping solution (amine solution) treatment, and a pattern forming method using the positive photosensitive resin composition, in particular, It is a problem to provide an excellent pattern formation method. Moreover, this invention makes it a subject to provide the manufacturing method by which the said positive photosensitive resin composition which has such a characteristic is obtained.

Moreover, this invention is a cured film obtained using such a positive photosensitive resin composition, The heat resistance and heat resistance in which high transmittance | permeability does not fall even by high temperature baking or a resist stripping liquid (amine-type solution) process are maintained, and transparency is maintained. It is an object of the present invention to provide a cured film excellent in chemical properties and various elements and materials made using such a cured film.

MEANS TO SOLVE THE PROBLEM This inventor came to the following as a result of earnestly researching in order to solve the said subject.

That is, it is a positive photosensitive resin composition containing the following (A) component, (B) component, (C) component, (D) component, and (E) solvent from a 1st viewpoint.

Component (A): having a functional group capable of achieving a thermal crosslinking reaction with a compound of component (B) and a functional group for curing the film that can achieve a thermal curing reaction with a compound of component (C) Alkali-soluble resins having a number average molecular weight of 2,000 to 30,000

(B) component: the compound which has 2 or more vinyl ether groups in 1 molecule

(C) component: the compound which has a 2 or more block isocyanate group in 1 molecule

(D) Component: photoacid generator

(E) solvent

As a 2nd viewpoint, the functional group for the said thermal crosslinking reaction is at least 1 sort (s) chosen from the group of a carboxyl group and a phenolic hydroxyl group, and the functional group for the said film hardening is an amino group which has hydroxyl groups and active hydrogens other than a phenolic hydroxyl group The positive photosensitive resin composition as described in a 1st viewpoint which is at least 1 sort (s) chosen from the group of the.

From a 3rd viewpoint, based on 100 mass parts of said (A) component, 1-80 mass parts of said (B) components, 1-80 mass parts of said (C) component, and 0.5-80 mass parts of said (D) The positive photosensitive resin composition as described in a 1st viewpoint or a 2nd viewpoint containing a component.

In 4th viewpoint, the positive photosensitive resin composition in any one of 1st viewpoint thru | or 3rd viewpoint which further contains alkali-soluble resin other than the said (A) component as (F) component.

In the fifth aspect, the forge type according to any one of the first to fourth aspects, wherein the amine compound is further contained 0.001 to 5 parts by mass based on 100 parts by mass of the component (A) as the component (G). Photosensitive resin composition.

In a sixth aspect, the positive photosensitive resin composition according to any one of the first to fifth aspects, wherein the (H) component further contains 0.2% by mass or less of the surfactant in the positive photosensitive resin composition.

In a seventh aspect, the step of applying the positive photosensitive resin composition according to any one of the first to sixth aspects to a semiconductor substrate, the step of irradiating the applied surface with ultraviolet light through a pattern mask, and developing the coated surface And a step of forming a pattern on the semiconductor substrate and performing a post bake for film curing on the pattern forming surface.

In a eighth aspect, the pattern forming method according to the seventh aspect, wherein the ultraviolet ray is light having at least one wavelength among i-rays, g-rays, and h-rays.

In a ninth aspect, the pattern forming method according to the seventh aspect, wherein the ultraviolet rays are ArF, KrF, or F ₂ laser light.

In a tenth aspect, the following components (A), (B), (C), (D) and (E) are mixed, and the mixed solution is maintained at a temperature higher than room temperature for a necessary period of time. The following thermal crosslinking reaction advances to some extent, and produces the positive photosensitive resin composition containing the crosslinked material of (A) component and (B) component in addition to (A) component-(D) component, The manufacturing method of a positive photosensitive resin composition.

Component (A): having a functional group capable of achieving a thermal crosslinking reaction with a compound of component (B) and a functional group for curing the film that can achieve a thermal curing reaction with a compound of component (C) Alkali-soluble resins having a number average molecular weight of 2,000 to 30,000

(B) component: the compound which has 2 or more vinyl ether groups in 1 molecule

(C) component: the compound which has a 2 or more block isocyanate group in 1 molecule

(D) Component: photoacid generator

(E) solvent

As a 11th viewpoint, the said mixed solution is hold | maintained at the temperature of 30-70 degreeC for 2 hours-5 days, The manufacturing method of the positive photosensitive resin composition as described in a 10th viewpoint.

From a 12th viewpoint, the functional group for thermal crosslinking reaction in the said (A) component is at least 1 sort (s) chosen from the group of a carboxyl group and a phenolic hydroxyl group, and the functional group for said film hardening is hydroxyl groups other than a phenolic hydroxyl group. And the method for producing a forged photosensitive resin composition according to the tenth or eleventh aspect, which is at least one selected from the group of amino groups having active hydrogen.

From a 13th viewpoint, based on 100 mass parts of said (A) components, 1-80 mass parts of said (B) components, 1-80 mass parts of said (C) components, and 0.5-80 mass parts of said (D) components The manufacturing method of the positive photosensitive resin composition in any one of 10th-12th viewpoint which contains.

From a 14th viewpoint, the manufacturing method of the positive photosensitive resin composition in any one of 10th-13th viewpoint which further contains alkali-soluble resin other than the said (A) component as (F) component.

In the fifteenth aspect, the forge type according to any one of the tenth to fourteenth aspects, wherein the amine compound is further contained 0.001 to 5 parts by mass based on 100 parts by mass of the component (A) as the component (G). The manufacturing method of the photosensitive resin composition.

In a sixteenth aspect, as a component (H), the surfactant further contains 0.2% by mass or less of the positive photosensitive resin composition produced by the production method according to any one of tenth to fifteenth aspects. The manufacturing method of the positive photosensitive resin composition in any one of a 15th viewpoint.

In a seventeenth aspect, using the forged photosensitive resin composition according to any one of the first to sixth aspects or the forged photosensitive resin composition prepared by the method according to any one of the tenth to sixteenth aspects Cured film obtained.

A liquid crystal display device having the cured film according to the eighteenth viewpoint from the eighteenth viewpoint.

19th viewpoint and the array planarization film for liquid crystal displays which consist of a cured film of 17th viewpoint.

An interlayer insulating film made of the cured film according to the seventeenth viewpoint from the twentieth viewpoint.

Microlens which consists of a cured film as described in a 17th viewpoint from 21st viewpoint.

To practice the invention  Optimal form for

[Posiform photosensitive resin composition]

The positive photosensitive resin composition of the present invention is an alkali-soluble resin of component (A), a compound having a vinyl ether group of component (B), a compound having a block isocyanate group of component (C), and a photoacid generator of component (D). And (E) a solvent, and if necessary, a composition containing another alkali-soluble resin of component (F), an amine compound of component (G), or a surfactant of component (H).

In addition, the positive photosensitive resin composition manufactured by the method of this invention is the said (A) component-(E) solvent other than the crosslinked body of (A) component and (B) component mentioned later, and (F) as needed. ) To component (H).

In addition, the compounding ratio of (A) component and (B) component is decided based on the compounding quantity in a mixing | blending stage, and thermal blending reaction advances to some extent by maintaining at elevated temperature after a compounding, (A) component When the crosslinked body of (B) component is formed, the sum of (A) component which forms a crosslinked body, and (A) component which does not participate in a bridge | crosslinking becomes a compounding quantity of (A) component, and a crosslinked body is similarly The sum of the component (B) forming the compound and the component (B) not involved in the crosslinking becomes a blending amount of the component (B).

Each component is explained in full detail below.

<A component>

The component (A) is in the structure of the resin between the functional group capable of performing thermal crosslinking reaction between the compound having a vinyl ether group of the component (B) and the compound having a block isocyanate group of the component (C). It is alkali-soluble resin which has a functional group for film | membrane hardening which can achieve a thermosetting reaction, and has a polystyrene conversion number average molecular weight (henceforth a number average molecular weight) 2,000-20,000.

The functional group for the thermal crosslinking reaction is a group capable of reacting with a vinyl ether group in the component compound (B) at an elevated temperature to thermally crosslink with the compound of the component (B) to form a resist film. Is at least 1 sort (s) chosen from the group of a carboxyl group and phenolic hydroxyl group.

Moreover, the functional group for film hardening of the (A) component and the (B) component of the thermal crosslinked body (in the exposed part, the decrosslinked body in which the thermal crosslinked product was further dissociated), It is a group which can harden | cure a film | membrane by making a crosslinking reaction through the isocyanate group which the block part dissociated between compounds, and the typical functional group is at least selected from the group of the hydroxyl group other than phenolic hydroxyl group, and the amino group which has active hydrogen. It is one kind. Here, the amino group which has active hydrogen means the primary or secondary amino group which can discharge | release hydrogen by reaction. Therefore, since an amide group does not have active hydrogen, it does not correspond to the amino group which has active hydrogen.

Resin of (A) component should just be alkali-soluble resin which has such a structure, and is not specifically limited about the main chain skeleton, the kind of side chains, etc. of the polymer which comprises resin.

In addition, resin of (A) component exists in the range of the number average molecular weight 2,000-30,000. If the number average molecular weight is over 30,000, developing residues tend to occur, and the sensitivity is greatly reduced, while if the number average molecular weight is too small, less than 2,000, a considerable amount of film reduction occurs during development, and curing There may be a shortage.

As alkali-soluble resin of (A) component, acrylic resin, polyhydroxy cystyrene-type resin, etc. are mentioned, for example. In particular, acrylic resin is more preferable because of its high transparency.

In addition, in this invention, alkali-soluble resin which consists of a copolymer (henceforth a specific copolymer) obtained by superposing | polymerizing a some kind of monomer can also be used as (A) component. In this case, the alkali-soluble resin of the component (A) may be a brand product of a plurality of specific copolymers.

That is, the specific copolymer, at least one monomer selected from the group of monomers having a functional group for thermal crosslinking reaction, that is, a monomer having at least one of a carboxyl group and a phenolic hydroxy group, and a functional group for film curing The copolymer which formed at least 1 sort (s) of monomer selected suitably from the group which has at least one of the monomer which has, ie, the hydroxyl group other than a phenolic hydroxyl group, and the amino group which has active hydrogen as an essential structural unit, The number average molecular weight 2,000 to 30,000.

Said "monomer which has at least one of a carboxyl group and phenolic hydroxy" includes the monomer which has a carboxyl group, the monomer which has a phenolic hydroxy group, and the monomer which has both a carboxyl group and a phenolic hydroxy group. These monomers are not limited to having one carboxyl group or phenolic hydroxy group, and may have two or more.

In addition, as said "monomer which has at least one of the hydroxyl group other than a phenolic hydroxyl group, and the amino group which has active hydrogen", the monomer which has a hydroxyl group other than a phenolic hydroxyl group, the monomer which has an amino group which has active hydrogen, and other than phenolic hydroxyl group The monomer which has both the hydroxyl group and the amino group which has active hydrogen of is contained. These monomers are not limited to having one hydroxy group other than a phenolic hydroxy group or an active hydrogen, and may have two or more.

Hereinafter, although the specific example of the said monomer is given, it is not limited to these.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, and mono- (2- (methacryloyloxy) ethyl) phthalate. , N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, and the like.

As a monomer which has a phenolic hydroxy group, hydroxy styrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide, etc. are mentioned, for example. Can be.

As a monomer which has hydroxyl groups other than a phenolic hydroxyl group, it is 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-acryloyloxy-6-hydroxy norbornene-2-cart, for example. Voxylic-6-lactone, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone Etc. can be mentioned.

Moreover, 2-aminoethyl acrylate, 2-aminomethyl methacrylate, etc. are mentioned as a monomer which has an amino group which has active hydrogen.

Moreover, the copolymer formed as a structural unit may also be a monomer other than the monomer which has a functional group for thermal crosslinking reaction, and the monomer which has a functional group for film hardening (henceforth other monomer).

The other monomer may specifically be copolymerizable with the monomer which has at least one of the monomer which has at least one of a carboxyl group and a phenolic hydroxyl group, and the amino group which has an hydroxyl group other than a phenolic hydroxyl group, and active hydrogen, (A The component is not particularly limited as long as the properties of the component are not impaired.

Specific examples of the other monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

As an acrylate ester compound, For example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2 , 2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxy ethyl acrylate, methoxy triethylene glycol acrylate, 2-ethoxy ethyl acrylate , Tetrahydroprryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acryl The rate, 8-ethyl-8- tricyclodecyl acrylate, etc. are mentioned.

As methacrylic acid ester compound, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, for example. , Phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, Methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydroprryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, and the like.

As a vinyl compound, vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether, etc. are mentioned, for example.

As a styrene compound, styrene, methyl styrene, chloro styrene, bromostyrene, etc. are mentioned, for example.

As a maleimide compound, maleimide, N-methyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, etc. are mentioned, for example.

Although the method of obtaining the specific copolymer used for this invention is not specifically limited, For example, at least 1 sort (s) of monomer chosen suitably from the group of the monomer which has at least one of a carboxyl group and a phenolic hydroxyl group, and other than a phenolic hydroxyl group 50-110 degreeC in a solvent at least 1 sort (s) of monomer chosen suitably from the group which has at least one of the amino group which has a hydroxyl group and active hydrogen, monomers other than the said monomer as needed, and a polymerization initiator etc. as needed. It is obtained by polymerizing under the temperature of. At this time, the solvent obtained will not be specifically limited if it melt | dissolves the monomer and specific copolymer which comprise a specific copolymer. As a specific example, the solvent described by the (E) solvent mentioned later is mentioned.

The specific copolymer obtained in this way is a solution state which this specific copolymer melt | dissolved in the solvent normally.

Furthermore, the specific copolymer solution obtained as mentioned above is thrown in again under stirring, such as diethyl ether, water, and reprecipitated, and the produced precipitate is filtered and washed, and is normal temperature or heat-dried under normal pressure or reduced pressure, It can be set as the powder of a specific copolymer. By such operation, the polymerization initiator and unreacted monomer which coexist with a specific copolymer can be removed, As a result, the refined powder of the specific copolymer can be obtained. When it cannot fully refine | purify by operation once, the obtained powder may be dissolved again in a solvent and the said operation may be repeated.

In this invention, the powder of a specific copolymer may be used as it is, or the powder may be redissolved with the same solvent as (E) solvent mentioned later, for example, and may be used in a solution state.

<B component>

The component (B) is a compound having two or more vinyl ether groups in one molecule. This should just be a compound which has 2 or more of 1 molecule of vinyl ether groups which can be thermally crosslinked with alkali-soluble resin of (A) component at normal pre bake temperature, and is not specifically limited about the kind and structure. .

The compound of this (B) component is isolate | separated from the alkali-soluble resin of (A) component by the acid generate | occur | produced by exposure in the presence of a photo-acid generator after thermal crosslinking with alkali-soluble resin of (A) component (decrosslinking) Then, alkali-soluble resin of (A) component is also removed by image development using alkaline developing solution. Therefore, as the compound of this species, a vinyl ether compound or the like generally used for a vinyl ether type chemically amplified resist component can be applied. In the case of using such a compound, it has the advantage that the shape of the film formed can be controlled by changing the compounding quantity of this compound and adjusting a thermal crosslinking density.

And as a compound of (B) component, the compound represented by Formula (1) and Formula (2) among a said vinyl ether type compound is especially preferable at the point which is developed without a residual film or residue in an exposure part.

(In formula, n is an integer of 2-10, k is an integer of 1-10, R <^1> represents n-valent organic group.)

(In formula, m shows the integer of 2-10.)

Although n of Formula (1) shows the number of vinyl ether groups in 1 molecule, as n, the integer of 2-4 is more preferable. And although m of Formula (2) also shows the number of vinyl ether groups in 1 molecule, as m, the integer of 2-4 is more preferable.

Specific examples of the compound represented by formulas (1) and (2) include bis (4- (vinyloxymethyl) cyclohexylmethyl) glutalate, tri (ethylene glycol) divinyl ether, adipic acid divinyl ester, Diethylene glycol divinyl ether, tris (4-vinyloxy) butyltrimerate, bis (4- (vinyloxy) butyl) terephthalate, bis (4- (vinyloxy) butylisophthalate, and cyclohexanedimethanoldi Vinyl ether etc. are mentioned.

Moreover, the compound of (B) component is 1-80 mass parts with respect to 100 mass parts of alkali-soluble resin of (A) component, Preferably it is used in the ratio of 5-40 mass parts. When the amount of the compound used in the component (B) is less than the lower limit of the above range, the film reduction in the unexposed portion becomes remarkable, and the relief shape of the pattern shape becomes poor. On the other hand, when the usage-amount of the compound of (B) component exceeds the upper limit of the said range, the sensitivity of a film | membrane will fall largely and residue between patterns will generate after image development.

<C component>

The component (C) is a compound having two or more blocked isocyanate groups in one molecule. This is, for example, a conventional post bake for a film made of an alkali-soluble resin of component (A) thermally crosslinked with or further decrosslinked with a compound of component (B). What is necessary is just a compound which has two or more of the block isocyanate groups which can be heat-hardened by temperature, and is not specifically limited about the kind and structure.

The compound of this component (C) has two or more of the block isocyanate groups in which one isocyanate group (-NCO) is blocked by a suitable protecting group, and when exposed to high temperatures at the time of heat curing, the protecting group (block portion) is heated. By dissociating and falling off, the crosslinking reaction proceeds between the functional groups (for example, hydroxy groups other than phenolic hydroxy groups and amino groups having active hydrogen) other than phenolic hydroxy groups with each other through the generated isocyanate groups. For example, equation (3)

(In formula, R <^2> represents the organic group of a block part.) The compound which has two or more of these molecules (this group may be the same, or may respectively differ).

The compound of (C) component which has two or more block isocyanate groups in 1 molecule can be obtained by, for example, acting a suitable blocking agent with respect to the compound which has 2 or more isocyanate groups in 1 molecule.

As a compound which has two or more isocyanate groups in 1 molecule, For example, isophorone diisocyanate, 1, 6- hexamethylene diisocyanate, methylenebis (4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, etc., or these Or a reactant of diols, triplets, or diols, triols, diamines, and triamines thereof.

Examples of the blocking agent include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol and cyclohexanol, phenol, phenols such as o-nitrophenol, p-chlorophenol, o-, m- or p-cresol, lactams such as ε-caprolactam, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime And oximes such as acetophenone oxime and benzophenone oxime, pyrazoles such as pyrazole, 3,5-dimethylpyrazole and 3-methylpyrazole, and thiols such as dodecanethiol and benzenethiol.

In the compound of component (C), thermal dissociation of the block portion occurs at a higher temperature than in the case of post-baking temperature, and crosslinking reaction proceeds through the isocyanate group, but at a lower temperature than in the case of prebaking temperature, crosslinking by the isocyanate group proceeds. It is especially preferable as the compound of the component (C) that the thermal dissociation temperature of the block portion is considerably higher than the prebaking temperature, for example, 120 ° C to 230 ° C.

As a compound of such (C) component, the following specific examples are mentioned, for example.

In the formula, the compound of the component (C) in which the isocyanate compound is derived from isophorone diisocyanate is more preferable in terms of heat resistance and coating film properties, and the following are mentioned as such compounds.

R in the following formula represents an organic group.

In this invention, the compound of (C) component may be used individually by 1 type, and may be used in combination of 2 or more type.

Moreover, the compound of (C) component is used in 1-80 mass parts with respect to 100 mass parts of alkali-soluble resin of (A) component, Preferably it is used in the ratio of 5-40 mass parts. If the amount of the compound used in the component (C) is less than the lower limit of the above range, the thermal curing is insufficient and a satisfactory cured film is not obtained, while if the amount of the compound used in the component (C) is an excessive amount exceeding the upper limit of the above range, The development is insufficient, resulting in development residues.

<D component>

(D) component is a photo-acid generator (PAG). This is to generate acid (sulfonic acid, carbonic acid, etc.) directly or indirectly by irradiation of light (ultraviolet rays such as g, h and i rays, ArF, KrF, F ₂ laser light or electron beam, etc.) used for exposure. It is a substance and if it has such a characteristic, the kind, structure, etc. are not specifically limited.

Examples of the photoacid generator of component (D) include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzoin citrate compounds, and iron arene (arene). ) Complexes, halogen-containing triazine compounds, acetphenone derivative compounds, and cyano group-containing oxime sulfonate compounds. Conventionally known or conventionally used photoacid generators are not particularly limited and can be applied in the present invention. In addition, in this invention, the photo-acid generator of (D) component may be used individually by 1 type, and may be used in combination of 2 or more type.

Specific examples of such a photoacid generator include the following. Of course, these compounds are a few examples of a very large number of applicable photoacid generators, and of course are not limited thereto.

Diphenyl iodonium chloride, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium mesylate, diphenyl iodide tsilate, diphenyl iodonium bromide, diphenyl iodonium tetrafluoroborate, diphenyl iodide Nium hexafluoro antimonate, diphenyl iodonium hexafluoro arsenate, bis (p-tert-butylphenyl) iodonium hexafluophosphate, bis (p-tert-butylphenyl) iodonium mesylate, bis (p-tert-butylphenyl) iodide tsilicate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium tetrafluoroborate, bis (p tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, Triphenylsulfonium Fluoromethanesulfonate, tri (p-methoxyphenyl) sulfoniumtetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (p-ethoxyphenyl) sulfoniumtetrafluoro Bororate, triphenylphosphonium chloride, triphenylphosphonium bromide, tri (p-methoxyphenyl) phosphoniumtetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexafluorophosphonate, tri (p-ethoxyphenyl) phosphoniumtetrafluoroborate,

In the present invention, one kind of photoacid generator selected from the group of compounds described above can be used alone, or two or more kinds of photoacid generators selected from the group of compounds described above can be used in combination.

In addition, the photo-acid generator of (D) component is 0.5-80 mass parts with respect to 100 mass parts of alkali-soluble resin of (A) component, Preferably it is used in the ratio of 1-30 mass parts. When the amount of the photoacid generator of component (D) is less than the lower limit of the above range, dissociation from component (B) component alkali-soluble resin thermally crosslinked during exposure does not proceed sufficiently, The relief of a pattern shape becomes difficult to be obtained, and on the other hand, when the usage-amount of the photo-acid generator of (D) component exceeds the upper limit of the said range, the storage stability of a positive photosensitive resin composition will fall.

<E solvent>

The (E) solvent used for this invention melt | dissolves (A) component-(D) component, and also melt | dissolves (F) component-(H) component etc. which are mentioned later added as needed, and such dissolving power As long as it has a solvent which has the solvent, the kind, structure, etc. are not specifically limited.

As such (E) solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, γ-butyrolactone, 2 Ethyl hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylfo Amide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

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

Among these (E) solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, and the like have good coating properties and stability. It is more preferable from a high viewpoint. These solvents are generally used as a solvent for photoresist materials.

<F component>

(F) component is alkali-soluble resin other than (A) component. As the positive photosensitive resin composition of this invention, alkali-soluble resin other than (A) component can be further contained unless the effect of this invention is impaired.

Preferably, (F) component contains 1 mass part-90 mass parts with respect to 100 mass parts of (A) component.

As such (F) component, acrylic resin and hydroxy styrene resin other than (A) component, a phenol novolak resin, a polyamide resin, a polyimide precursor, a polyimide resin, etc. are mentioned, for example.

<G component>

(G) A component is an amine compound. The positive photosensitive resin composition of the present invention may further contain an amine compound as long as the effect of the present invention is not impaired for the purpose of increasing its storage stability.

Although there is no restriction | limiting in particular as an amine compound of (G) component, For example, a triethanolamine, a tributanolamine, a trimethylamine, a triethylamine, a trinormal amine, a triisopropyl amine, a trinormal butylamine, and a tri- tertiary amines such as tert-butylamine and diazabicyclooctane; aromatic amines such as pyridine and 4-dimethylaminopyridine; and further, primary amines such as benzylamine and normal butylamine, and diethylamine. And secondary amines such as dinormalbutylamine.

The amine compound of (G) component can be used individually by 1 type or in combination of 2 or more types.

When an amine compound is used, the content is 0.001-5 mass parts with respect to 100 mass parts of alkali-soluble resin of (A) component, Furthermore, it is 0.005-1 mass part in some cases, Preferably it is 0.01 0.5 mass parts. When the usage-amount of the amine compound of (G) component is less than the lower limit of the said range, the storage safety of a positive photosensitive resin composition cannot fully be improved, while the usage-amount of the amine compound of (G) component is the upper limit of the said range. If it is an excessive amount exceeding, the sensitivity of a positive photosensitive resin composition may fall.

<H component>

(H) A component is surfactant. As the positive photosensitive resin composition of this invention, surfactant can be further contained as long as the effect of this invention is not impaired for the purpose of improving the applicability | paintability.

Although it does not specifically limit as surfactant of (H) component, For example, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned. As this kind of surfactant, commercial items, such as Sumitomo 3M Co., Ltd., Dai Nippon Inky Chemical Co., Ltd. product, or Asahi Glass Co., Ltd. product, can be used, for example. These commercial items are convenient because they can be easily obtained. Specific examples thereof include F-top EF301, EF303, EF352 (manufactured by Gemco), Megapak F171, F173 (manufactured by Dainippon Inky Chemical Co., Ltd.), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.). And fluorine-based surfactants such as Asahigard AG710, Saffron S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.).

Surfactant of (H) component can be used individually by 1 type or in combination of 2 or more types.

When surfactant is used, the content is 0.2 mass% or less normally in 100 mass% of positive photosensitive resin compositions, Preferably it is 0.1 mass% or less. Even when the usage-amount of surfactant of (H) component is set to the quantity exceeding 0.2 mass%, the improvement effect of the said applicability | paintability becomes slow and it is uneconomical.

<Other additives>

In addition, the forge-type photosensitive resin composition of this invention is an adhesive adjuvant, such as a rheology control agent and a silane coupling agent, a pigment, a dye, a storage stabilizer, an antifoamer, or a polyhydric phenol as needed, unless the effect of this invention is impaired. And a dissolution accelerator such as polyvalent carbonic acid.

<Posiform photosensitive resin composition>

The positive type photosensitive resin composition of this invention is alkali-soluble resin of (A) component, the compound which has a vinyl ether group of (B) component, the compound which has a block isocyanate group of (C) component, the photoacid generator of (D) component, and (E) A solvent, and if necessary, each of one or more of another alkali-soluble resin of component (F), an amine compound of component (G), a surfactant of component (H), and other additives It is a composition which can contain further.

Among these, the preferable example of the positive photosensitive resin composition of this invention is as follows.

[1]: Based on 100 parts by mass of the component (A), 1 to 80 parts by mass of the component (B), 1 to 80 parts by mass of the (C) component, and 0.5 to 80 parts by mass of the component (D) are contained. The positive photosensitive resin composition in which the component melt | dissolved in the (E) solvent.

[2]: The composition of [1], wherein the positive photosensitive resin composition further contains 1 to 90 parts by mass based on 100 parts by mass of the component (F).

[3]: The composition of [1] or [2], wherein the positive photosensitive resin composition further contains 0.001 to 5 parts by mass based on 100 parts by mass of the component (G).

[4]: The positive photosensitive resin composition containing 0.2 mass% or less of (H) component further in the said positive photosensitive resin composition of [1], [2], or [3].

Although the ratio of solid content in the positive photosensitive resin composition of this invention is not specifically limited as long as each component is melt | dissolving in a solvent uniformly, For example, it is 1-80 mass%, For example, 5-60 It is mass% or 10-50 mass%. Here, solid content means what remove | excluding the (E) solvent from all the components of a positive photosensitive resin composition.

[Method for Producing Posiform Photosensitive Resin Composition]

Although the manufacturing method of the positive photosensitive resin composition of this invention is not specifically limited, As the manufacturing method, (A) component (alkali-soluble resin) is melt | dissolved in the (E) solvent, for example, in this solution (B ) Component (compound having two or more vinyl ether groups in one molecule), (C) component (compound having two or more block isocyanate groups in one molecule), (D) component (photoacid generator) and (H) component (interface) Activator) is mixed at a predetermined ratio and made into a homogeneous solution, or in a suitable step of this preparation method, if necessary, (G) component (amine compound), (F) component (other alkali-soluble resin) and / or The method of adding and adding another additive further is mentioned.

In preparation of the positive photosensitive resin composition of this invention, the specific copolymer solution obtained by the polymerization reaction in (E) solvent can be used as it is, and in this case, it is the same as the above in the solution of this (A) component (B). When ()) component, (C) component, etc. are put and it is set as a uniform solution, you may add (E) solvent further for the purpose of concentration adjustment. At this time, the solvent (E) used in the formation process of a specific copolymer and the solvent (E) used for density | concentration adjustment at the time of preparation of a positive photosensitive resin composition may be the same, and may differ.

And it is preferable to use the prepared solution of the forge-type photosensitive resin composition after filtering using the filter etc. which have a pore diameter of about 0.2 micrometer.

Preferably, in the said preparation method, by holding the mixed solution containing (A) component (E) solvent and (F) component-(H) component as needed under the temperature higher than room temperature for a predetermined period, The following thermal crosslinking reaction advances to some extent, and in addition to (A) component-(E) solvent and (F) component-(H) component as needed, the crosslinked body of (A) component and (B) component is carried out. It is preferable to obtain the positive photosensitive resin composition to contain.

Also preferably, the mixed solution is kept at 30 to 70 ° C. for 2 hours to 5 days, thereby adding to the component (A) to the solvent (E) and, if necessary, the component (F) to the component (H). The positive photosensitive resin composition containing the crosslinked body of (A) component and (B) component is obtained.

By preparing on the said temperature and time conditions, the uniformity of the resin composition obtained becomes high and this leads to the remarkable sensitivity improvement of the film | membrane obtained by disperse | distributing efficiently a photoacid generator in a film | membrane when it provides to the subsequent film-forming process.

If the stirring temperature is higher than 70 ° C., the crosslinking reaction or the curing reaction proceeds, the composition becomes nonuniform, and the sensitivity of the obtained film is greatly lowered. If the stirring temperature is lower than 30 ° C., the uniformity of the composition is not obtained and the sensitivity is improved. It does not lead.

[Production method of coating film, pattern formation and cured film]

The positive photosensitive resin composition of the present invention may be a semiconductor substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a metal, for example, a substrate coated with aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, etc.). , ITO substrate, etc.), by spin coating, flow coating, roll coating, slit coating, slit followed by spin coating, ink jet coating, and the like, and then preliminarily drying with a hot plate or an oven to form a coating film. can do. Then, a positive photosensitive resin film is formed by heat-processing this coating film.

As this heat processing condition, the selected heating temperature and heating time suitably are employ | adopted, for example in the range of temperature 70 degreeC-160 degreeC, and time 0.3-60 minutes. 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 positive photosensitive resin film formed from the positive photosensitive resin composition is, for example, 0.1 to 50 µm, and further, for example, 0.3 to 30 µm, and for example, 0.5 to 10 [Mu] m.

And the formed positive photosensitive resin film becomes a film | membrane which is hard to melt | dissolve in an alkaline developing solution by crosslinking the compound which has a vinyl ether group of (B) component to resin of (A) component by the heat processing at the time of formation. In this case, when the heat treatment temperature is lower than the lower limit of the temperature range, thermal crosslinking becomes insufficient, and film reduction may occur in the unexposed portion. In addition, when the heat treatment temperature is too high beyond the upper limit of the above temperature range, the thermal crosslinked portion once formed may be cut again, causing film reduction in the unexposed portion.

When the positive photosensitive resin film formed from the positive photosensitive resin composition of the present invention is exposed by irradiation with ultraviolet rays, ArF, KrF, F ₂ laser light or the like using a mask having a predetermined pattern, the positive photosensitive resin film is exposed in the positive photosensitive resin film. By the action of the acid generated in the photoacid generator (PAG) of the component (D) to be included, the exposed portion of the film becomes soluble in the alkaline developer.

The exposure is preferably carried out by an i-line, g line and h light having a wavelength of at least one kind of a line, or ArF, KrF or F ₂ laser light.

Next, post-exposure heating (PEB) is performed with respect to the positive photosensitive resin film. As heating conditions in this case, an appropriately selected heating temperature and heating time are employed in the range of temperature 80 ° C to 150 ° C and time for 0.3 to 60 minutes.

Then, image development is performed using alkaline developing solution. As a result, the exposed portion of the positive photosensitive resin film is removed, and a pattern-shaped relief is formed.

As an alkaline developer that can be used, for example, an aqueous solution of an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, aqueous solution of quaternary ammonium hydroxide such as choline, ethanolamine, propylamine And alkaline aqueous solutions, such as aqueous amine solutions, such as ethyleneamine. And a surfactant etc. can also be added to these developing solutions.

In the above, the tetraethylammonium hydroxide 0.1-2.38 mass% aqueous solution is generally used as a developing solution of a photoresist, and also develops satisfactorily, without causing a problem, such as swelling, also in this photosensitive resin composition of this invention. can do.

As the developing method, any of a liquid method, a dipping method, a rocking deposition method and the like can be used. The developing time at this time is 15 to 180 second normally.

After the development, washing with running water is carried out on the positive photosensitive resin film, for example, for 20 to 90 seconds, followed by air drying using compressed air or compressed nitrogen or by spinning to remove moisture on the substrate. Thus, a patterned film is obtained.

Next, the pattern forming film is subjected to post-baking for thermal curing, specifically, by heating using a hot plate, an oven, or the like, thereby providing heat resistance, transparency, planarization, and low water absorption. The film which is excellent in chemical resistance, etc., and has a favorable relief pattern is obtained.

 As a post-baking, the method of processing for 5 to 30 minutes on a hotplate and 30 to 90 minutes in an oven is generally employ | adopted at the heating temperature selected from the temperature range of 140 to 250 degreeC.

And by such a post-baking, the cured film which has the target favorable pattern shape can be obtained.

As mentioned above, with the positive photosensitive resin composition of this invention, the film | membrane reduction of the unexposed part at the time of image development is very small enough, and can form a coating film which has a fine pattern.

Moreover, the cured film obtained by this coating film is excellent in heat resistance, solvent resistance, and transparency.

In addition, when this kind of cured film is used as an array planarizing film for a liquid crystal display, for example, in a subsequent step, it is exposed under heating at a higher temperature (for example, 250 ° C.) during metal deposition, and in some cases, Long-time baking of high temperature (for example, 230 degreeC) is performed, and at the time of resist peeling after an etching, it is put in contact with the resist stripping liquid which is an amine solution, such as monoethanolamine (MEA). Therefore, such a cured film is required to have high resistance to high temperature baking (or long time baking) and to resist stripping liquid (amine solution) treatment.

In the cured film obtained by the present invention, the transmittance does not decrease even by high temperature baking (or long time baking) or by a resist stripping solution (amine solution), and high transparency is maintained and the film thickness is also reduced. And a cured film having excellent heat resistance and chemical resistance, and therefore, not only an array planarizing film of a TFT type liquid crystal element, but also various films in liquid crystal or organic EL display, for example, interlayer insulating film, protective film, insulating film, uneven film under reflective film, etc. It is suitable for the use of, and can be suitably used as a micro lens by selecting the shape of the cured film.

EXAMPLE

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

[Abbreviations used in Examples]

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

MAA: methacrylic acid

MMA: Methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

CHMI: N-cyclohexylmaleimide

NHPMA: N-hydroxyphenyl methacrylate

PEMA: Mono- (2- (methacryloyloxy) ethyl) phthalate

AIBN: azobisisobutylonitrile

PGMEA: propylene glycol monomethyl ether acetate

PGME: Propylene Glycol Monomethyl Ether

PAG1: CGI1397 (brand name) made in Chiba specialty chemicals

PAG2: TPS105 (brand name) made by Midori Chemical Co., Ltd.

PVE1: tris (4-vinyloxy) butyl) trimellitate

PVE2: triethylene glycol divinyl ether

PVE3: 1,4-cyclohexane dimethanol divinyl ether

NCO1: VESTAGON (registered trademark) B1065 (brand name) made in Degusa AG

NCO2: VESTAGON (registered trademark) BF1540 (brand name) made in Degusa AG

R30: Megapak R-30 (brand name) made by Dainippon Inkki Chemical Co., Ltd.

MEA: monoethanolamine

GT4: GT-401 (brand name) made by Daicel Chemical Industries, Ltd.

MPTS: γ-methacryloxypropyltrimethoxysilane

P200: 1 mol of P-200 (brand name) 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1methylethyl] phenyl] ethylidene] bisphenol by Toyo Synthetic Industries, Ltd. Photosensitizer synthesized by condensation reaction with 2 moles of 1,2-naphthoquinone-2-diazido-5-sulfonylchloride

[Measurement of number average molecular weight and weight average molecular weight]

The number average molecular weight and the weight average molecular weight of the alkali-soluble resin (specific copolymer) obtained according to the following synthesis examples were obtained by using the GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by Nippon Spectroscopy Co., Ltd. Tetrahydrofuran was measured under the conditions which flow in a column (column temperature 40 degreeC), and melt | dissolve at a flow volume of 1 ml / min. In addition, the following number average molecular weight (henceforth Mn) and a weight average molecular weight (henceforth Mw) are represented by polystyrene conversion value.

[Synthesis of Specific Copolymer]

Synthesis Example 1

As a monomer component which comprises the specific copolymer which is (A) component, MAA 15.5g, CHMI 35.3g, HEMA 25.5g, MMA 23.7g are used, AIBN 5g is used as a radical polymerization initiator, These are used in 200g of solvent PGMEA. The polymerization reaction at a temperature of 60 ° C to 100 ° C yielded a solution (specific copolymer concentration: 27.5 mass%) of component (A) (specific copolymer) of Mn 4,100 and Mw 7,600. (P1)

<Synthesis Examples 2 to 5>

Polymerization reaction was carried out in accordance with the same procedures and conditions as in Synthesis Example 1, using the monomer components and the solvents described in each column of Synthesis Example 2 to Synthesis Example 5 in Table 1 below, instead of the monomer component and the solvent used in Synthesis Example 1. Thereby, each solution (P2 to P6) of (A) component (specific copolymer) was obtained, and Mn and Mw of each specific copolymer obtained were measured.

Table 1 shows the measurement results of each monomer component and the molecular weight used in Synthesis Examples 1 to 6.

Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Specific copolymer solutions P1 P2 P3 P4 P5 P6 Monomer MAA (g) 15.5 13.5 17.5 15.5 CHMI (g) 35.3 11.8 35.3 35.7 HEMA (g) 25.5 25.5 26.0 25.5 MMA (g) 23.7 49.2 21.7 26.0 49.2 NHPMA (g) 41.2 41.2 PEMA (g) 32.6 32.6 Solvent ^{* 1} PGMEA (g) 200 200 200 200 PGME (g) 200 200 Number average molecular weight (Mn) 4,100 4,200 4,800 4,200 4,800 4,200 Weight average molecular weight (Mw) 7,600 7,300 9,300 7,300 8,700 7,500 Specific copolymer concentration (mass%) 27.5 40.5 23.0 32.5 23.0 28.0

* 1: Solvent used for the synthesis of a specific copolymer

[Preparation and Performance Test of Forged Photosensitive Resin Composition: 1]

<Examples 1 to 10, Comparative Examples 1 to 4>

According to the composition shown in following Table 2, (B) component, (C) component, (D) component and (E) solvent, and (G) component-(H) component are predetermined | prescribed to the solution of (A) component The positive photosensitive resin composition of each Example and each comparative example was prepared by mixing in a ratio and stirring at room temperature for 3 hours to make a uniform solution.

Comparative Example 5

To 5.5 g of the specific copolymer (P1) solution obtained in Synthesis Example 1 as the alkali-soluble resin solution, 1.1 g of P200 as the 1,2-quinonediazido compound, 1.1 g of GT4 as the epoxy-based crosslinking compound, R30 as the surfactant The positive photosensitive resin composition of Comparative Example 5 was prepared by adding 0.0039 g of MPTS, 0.25 g of MPTS as an adhesion aid, and 25.6 g of PGMEA as a solvent, and stirring the mixture at room temperature for 8 hours to form a uniform solution. It prepared.

Solution (g) of component (A) (B) Component (g) (C) component (g) (D) component (g) (E) Solvent (g) (G) component (g) (H) component (g) Example 1 P1 20.0 PVE1 1.11 NCO1 0.55 PAG1 0.28 PGMEA 2.9 - R30 0.0037 Example 2 P1 20.0 PVE1 0.83 NCO1 0.55 PAG1 0.28 PGMEA 2.8 - R30 0.0036 Example 3 P1 20.0 PVE1 0.56 NCO1 0.55 PAG1 0.28 PGMEA 1.6 - R30 0.0034 Example 4 P1 20.0 PVE1 1.11 NCO1 0.83 PAG1 0.28 PGMEA 3.5 - R30 0.0039 Example 5 P1 20.0 PVE1 1.11 NCO2 0.55 PAG1 0.28 PGMEA 2.9 - R30 0.0037 Example 6 P1 20.0 PVE1 1.11 NCO1 0.55 PAG1 0.28 PGMEA 2.9 TEA 0.055 R30 0.0038 Example 7 P2 13.6 PVE1 1.11 NCO1 0.55 PAG1 0.28 PGMEA 9.3 - R30 0.0037 Example 8 P3 23.9 PVE1 1.11 NCO1 0.55 PAG1 0.28 PGME / PGMEA 0.57 / 3.3 - R30 0.0037 Example 9 P1 20.0 PVE2 1.11 NCO1 0.55 PAG1 0.28 PGMEA 2.9 - R30 0.0037 Example 10 P1 20.0 PVE3 1.11 NCO1 0.55 PAG1 0.28 PGMEA 2.9 - R30 0.0037 Comparative Example 1 P5 23.9 PVE1 1.11 NCO1 0.55 PAG1 0.28 PGME / PGMEA 0.57 / 3.3 - R30 0.0037 Comparative Example 2 P6 19.6 PVE1 1.11 NCO1 0.55 PAG1 0.28 PGMEA 3.3 - R30 0.0037 Comparative Example 3 P1 20.0 PVE1 1.11 - PAG1 0.28 PGME 1.6 - R30 0.0034 Comparative Example 4 P1 20.0 - NCO1 0.55 PAG1 0.28 PGMEA 0.3 - R30 0.0032

For each of the positive photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 5 obtained, the sensitivity, the film reduction (in the unexposed part), the light transmittance (transparency) after the high temperature baking, the light transmittance after the MEA treatment, and the MEA, respectively Each item of resistance and dimensional accuracy was evaluated in the following order.

In addition, when obtaining a cured film from a positive photosensitive resin composition, about the comparative example 5, after image development, photo-bleaching is performed in the pre-baking stage, while about Example 1-10 and Comparative Examples 1-4, this photo is After exposure, post-exposure heating (PEB) is performed at the pre-development stage without exposure, and in this respect, the evaluation procedure of both is different as follows.

[Evaluation of sensitivity]

<Examples 1 to 10, Comparative Examples 1 to 4>

After the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, prebaking was performed on a hot plate at a temperature of 120 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. The film thickness was measured using F20 made from FILMETRICS. The coating film was irradiated with ultraviolet light having a light intensity of 5.5 mW / cm ² at 365 nm for a predetermined time by Canon ultraviolet irradiation device PLA-600FA, followed by post-exposure heating (PEB) on a hot plate at a temperature of 110 ° C. for 120 seconds. It was. Thereafter, the film was developed by immersing in 0.4% by mass of tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution for 60 seconds, followed by flowing water for 20 seconds with ultrapure water. The minimum exposure amount (mJ / cm <^2> ) by which the debris melt | dissolved in the exposure part was made into the sensitivity.

Comparative Example 5

After the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, prebaking was performed on a hot plate at a temperature of 120 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. The film thickness was measured using F20 made from FILMETRICS. This coating film was irradiated with ultraviolet light of 5.5 mW / cm ² at a light intensity of 365 nm by Canon ultraviolet irradiation device PLA-600FA. After developing for 60 seconds by immersing in 0.4 mass% of TMAH aqueous solution for 60 second, it flow-washed with ultrapure water for 20 second. The minimum exposure amount (mJ / cm <^2> ) by which the debris melt | dissolved in the exposure part was made into sensitivity.

[Evaluation of Membrane Reduction]

After the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, prebaking was performed on a hot plate at a temperature of 120 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. This film was immersed in 0.4 mass% of TMAH aqueous solution for 60 second, and the water was washed with ultrapure water for 20 second. Next, the film reduction degree of the unexposed part by the development was evaluated by measuring the thickness of this film. The film thickness in this evaluation was measured using F20 made from FILMETRICS.

[Evaluation of Light Transmittance (Transparency) after High Temperature Firing]

<Examples 1 to 10, Comparative Examples 1 to 4>

The positive photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 120 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. This coating film was immersed in 0.4 mass% of TMAH aqueous solution for 60 second, and it washed with water for 20 seconds with ultrapure water. Next, post-baking was performed by heating at 230 degreeC for 30 minutes, and the cured film with a film thickness of 1.9 micrometers was formed. The transmittance | permeability of 400 nm wavelength was measured for this cured film using the ultraviolet-visible spectrophotometer (The SIMADSU UV-2550 model number by Shimadzu Corporation). And after heating this coating film at 250 degreeC for 30 minutes, the transmittance | permeability of 400 nm wavelength was measured. The film thickness in this evaluation was measured using F20 made from FILMETRICS.

Comparative Example 5

After the positive photosensitive resin composition was applied on a quartz substrate using a spin coater, prebaking was performed on a hot plate at a temperature of 120 ° C. for 120 seconds to form a coating film having a thickness of 2.4 μm. This coating film was immersed in 0.4 mass% of TMAH aqueous solution for 60 second, and it washed with water for 20 seconds with ultrapure water. The coating film was irradiated with ultraviolet light having a light intensity of 5.5 mW / cm ² at 800 mJ / cm ² (photo-bleaching) at 365 nm by Canon ultraviolet irradiation device PLA-600FA, followed by heating at 230 ° C. for 30 minutes. It prebaked and the cured film with a film thickness of 1.9 micrometers was formed. The transmittance | permeability of 400 nm wavelength was measured for this cured film using the ultraviolet-visible spectrophotometer (The SIMADSU UV-2550 model number by Shimadzu Corporation). And after heating this coating film at 250 degreeC for 30 minutes, the transmittance | permeability of 400 nm wavelength was measured. The film thickness in this evaluation was measured using F20 made from FILMETRICS.

[Evaluation of Light Transmittance and MEA Resistance after MEA Treatment]

<Examples 1 to 10, Comparative Examples 1 to 4>

The positive photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 120 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. This coating film was immersed in 0.4 mass% of TMAH aqueous solution for 60 second, and it washed with water for 20 seconds with ultrapure water. Next, it post-baked by heating at 230 degreeC for 30 minutes, and the cured film with a film thickness of 1.9 micrometers was formed. This coating film was immersed in monoethanolamine heated to 60 degreeC for 20 minutes, and it washed with pure water for 20 second. And after drying on a hotplate for 10 minutes at the temperature of 180 degreeC, the transmittance | permeability of 400 nm wavelength was measured using the film thickness measurement and the ultraviolet-visible spectrophotometer (The SIMADSU UV-2550 model number by Shimadzu Corporation). The film thickness in this evaluation was measured using F20 made from FILMETRICS. MEA resistance (circle) and the thing which reduced the film thickness after postbaking, and the film thickness change after MEA treatment and drying were made into x.

Comparative Example 5

After the positive photosensitive resin composition was applied on a quartz substrate using a spin coater, prebaking was performed on a hot plate at a temperature of 120 ° C. for 120 seconds to form a coating film having a thickness of 2.4 μm. This coating film was immersed in 0.4 mass% of TMAH aqueous solution for 60 second, and it washed with water for 20 seconds with ultrapure water. The coating film was irradiated with ultraviolet light having a light intensity of 5.5 mW / cm ² at 800 mJ / cm ² (photo-bleaching) at 365 nm by Canon ultraviolet irradiation device PLA-600FA, followed by heating at 230 ° C. for 30 minutes. It post-baked and the cured film with a film thickness of 1.9 micrometers was formed. This coating film was immersed in monoethanolamine heated to 60 degreeC for 20 minutes, and it washed with pure water for 20 second. Subsequently, after drying on a hot plate for 10 minutes at 180 degreeC, the transmittance | permeability of 400 nm wavelength was measured using the film thickness measurement and the ultraviolet-visible spectrophotometer (Model SIMADSU UV-2550 by Shimadzu Corporation). The film thickness in this evaluation was measured using F20 made from FILMETRICS. MEA resistance (circle) and the thing which reduced the film thickness after postbaking, and the film thickness change after MEA treatment and drying were made into x.

[Dimension Accuracy]

<Examples 1 to 10, Comparative Examples 1 to 4>

After the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, prebaking was performed on a hot plate at a temperature of 120 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. The film thickness was measured using F20 made from FILMETRICS. Canon PLA-600FA the ultraviolet irradiation apparatus is the light intensity at 365nm 5.5mW / 40mJ / cm ² of ultraviolet light of ² cm in the parameter mask for line and space pattern of 8㎛ by irradiation to the coated film, and then the temperature 110 ℃ Post-exposure heating (PEB) was performed on a hot plate for 120 seconds at. Subsequently, after developing by immersing in 0.4 mass% of TMAH aqueous solution for 60 second, it flow-washed with ultrapure water for 20 second. Then, post-baking was performed on the hotplate for 30 minutes at 230 degreeC. The formed cross section was observed using a scanning electron microscope (hereinafter referred to as SEM) to measure the line width. (Circle) that the pattern width is 8 micrometers, and the thing which does not hold | maintain 8 micrometers by expanding or contracting the pattern width was made into x.

Comparative Example 5

After the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, prebaking was performed on a hot plate at a temperature of 120 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. The film thickness was measured using F20 made from FILMETRICS. This coating film was irradiated with 200 mJ / cm <^2> of ultraviolet-rays with a light intensity of 5.5 mW / cm <^2> at 365 nm through the mask of a line-and-space pattern of 8 micrometers by Canon ultraviolet irradiation device PLA-600FA. Subsequently, after developing by immersing in 0.4 mass% of TMAH aqueous solution for 60 second, it flow-washed with ultrapure water for 20 second. Then, post-baking was performed on the hotplate for 30 minutes at 230 degreeC. The formed pattern cross section was observed using SEM and the line width was measured. (Circle) that the pattern width is 8 micrometers, and the thing which does not hold | maintain 8 micrometers by expanding or contracting the pattern width was made into x.

[Evaluation results]

The results of the above evaluation are shown in Table 3 below.

Sensitivity (mJ / cm ² ) Membrane Reduction ^* (μm) Transmittance (%) MEA immunity Dimensional precision 230 ℃ / 30 minutes 250 ° C / 30 minutes After MEA treatment Example 1 23 none 91 91 91 ○ ○ Example 2 23 none 91 91 91 ○ ○ Example 3 23 none 91 91 91 ○ ○ Example 4 30 none 91 91 91 ○ ○ Example 5 27 none 91 91 91 ○ ○ Example 6 35 none 90 90 90 ○ ○ Example 7 23 none 91 91 91 ○ ○ Example 8 23 none 90 90 90 ○ ○ Example 9 23 none 91 91 91 ○ ○ Example 10 23 none 91 91 91 ○ ○ Comparative Example 1 23 none 90 90 90 × × Comparative Example 2 23 none 91 91 91 × × Comparative Example 3 23 none 90 90 90 × × Comparative Example 4 23 disappearance - - - × × Comparative Example 5 80 0.2 92 85 86 ○ ○

* `` No film reduction '' means that no film reduction was observed in the measurement results.

As can be seen from the results shown in Table 3, for Examples 1 to 10, all of them were highly sensitive, and no film reduction in the unexposed part was observed, and even after 30 minutes of high temperature baking at 250 ° C (or 230 ° C), The fall was small, high transparency was maintained, and further, even after the MEA treatment, there was little fall in the transmittance, and it had excellent MEA resistance and dimensional accuracy.

On the contrary, about Comparative Examples 1-3, the pattern formation film was reflowed by 230 degreeC and 30 minute postbaking, and the pattern of a desired shape and a dimension was not obtained. In addition, the film | membrane in which the pattern was not formed also reduced by the MEA process after 230 degreeC and 30 minute post-baking. The film thickness after the MEA treatment was reduced by about 25% from the film thickness before the MEA treatment. In addition, "transmittance after a MEA process" of Table 3 is a value with respect to the film | membrane which the film | membrane reduction after MEA process produced.

In Comparative Example 4, the film dissolved and disappeared due to development.

And about the comparative example 5, the film reduction amount in the unexposed part at the time of image development was 0.2 micrometer. After 230 ° C. and 30 minutes of post-baking, the membrane's transmittance was 91%, but when baked at 250 ° C. for 30 minutes, the membrane's transmittance decreased to 85%. In addition, after MEA treatment after 230 degreeC and 30 minute post-baking, the transmittance | permeability of a membrane fell from 91% to 86%.

[Preparation and Performance Test of Forged Photosensitive Resin Composition: 2]

<Examples 11-13, Comparative Examples 6-9>

According to the composition shown in following Table 4, to the specific polymer solution (P1, P4, and P6) obtained by carrying out similarly to the synthesis example mentioned above with the solution of (A) component, (B) component, (C) component, (D The positive photosensitive resin composition of each Example and each comparative example was prepared by mixing a) component, (E) solvent, and (H) component in a predetermined ratio, and stirring at room temperature for 3 hours to make a uniform solution. .

Solution (g) of component (A) (B) Component (g) (C) component (g) (D) component (g) (E) Solvent (g) (H) component (g) Example 11 P1 20.0 PVE1 0.83 NCO2 0.55 PAG2 0.22 PGMEA 17.8 R30 0.0025 Example 12 P4 16.9 PVE1 0.83 NCO1 0.55 PAG2 0.22 PGMEA 20.9 R30 0.0025 Example 13 P1 20.0 PVE2 0.83 NCO2 0.55 PAG2 0.19 PGMEA 18.0 R30 0.0025 Comparative Example 6 P6 19.6 PVE1 1.11 NCO1 0.55 PAG2 0.28 PGMEA 19.8 R30 0.0037 Comparative Example 7 P1 20.0 PVE1 1.11 - PAG2 0.28 PGME 16.9 R30 0.0034 Comparative Example 8 P1 20.0 - NCO1 0.55 PAG2 0.28 PGMEA 14.3 R30 0.0032 Comparative Example 9 P1 20.0 - GT4 1.1 P200 1.1 PGMEA 20.6 R30 0.0039

For each of the positive photosensitive resin compositions of Examples 11 to 13 and Comparative Examples 6 to 9 obtained, for each item of film reduction (in unexposed parts), resolution, and film thickness change after MEA treatment, respectively, Evaluation was performed accordingly.

[Evaluation of Membrane Reduction]

After the positive photosensitive resin composition was applied onto the silicon wafer using a spin coater, prebaking was performed on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 0.5 μm. This film was immersed in 0.4 mass% of TMAH aqueous solution for 60 second, and it washed with water for 20 seconds with ultrapure water. Next, by measuring this film thickness, the film reduction degree of the unexposed part by development was evaluated. The film thickness in this evaluation was measured using F20 made from FILMETRICS.

[resolution]

An antireflection film solution for KrF (DUV-30J (trade name) manufactured by Nissan Chemical Co., Ltd.) was applied onto a silicon wafer using a spin coater, and then fired on a hot plate at a temperature of 205 ° C. for 60 seconds to obtain a film thickness of 140 nm. An antireflection film was formed. After apply | coating the positive photosensitive resin composition on this antireflection film using a spin coater, it baked on the hotplate for 90 second at the temperature of 110 degreeC, and formed the coating film of 0.5 micrometer in thickness. 10 mJ / cm <^{2> of} this coating film was irradiated with KrF excimer laser reduction projection exposure apparatus (NSR-201A by Nikon Corporation) via the mask of a line-and-space pattern, and then exposed on a hotplate for 90 seconds at the temperature of 110 degreeC. Heating (PEB) was performed. Subsequently, after developing by immersing a 0.4 mass% TMHA aqueous solution for 60 second, it washed with water for 20 seconds with ultrapure water. Thereafter, post-baking was performed on a hot plate at 230 ° C. for 30 minutes. The cross section of the formed pattern was observed with the scanning electron microscope (henceforth SEM), and the line width was measured. The minimum pattern size resolved to the mask size without residue between patterns was taken as the resolution.

[Evaluation of MEA Resistance]

After the positive photosensitive resin composition was applied onto a quartz substrate using a spin coater, prebaking was performed on a hot plate at a temperature of 110 ° C. for 90 seconds to form a coating film having a thickness of 0.5 μm. This coating film was immersed in 0.4 mass% of TMAH aqueous solution for 60 second, and it washed with water for 20 seconds with ultrapure water. Next, post-baking was performed by heating at 230 degreeC for 30 minutes, and the cured film with a film thickness of 0.4 micrometer was formed. This coating film was immersed in monoethanolamine heated to 60 degreeC for 20 minutes, and it washed with pure water for 20 second. And after drying on a hotplate for 10 minutes at 180 degreeC, the film thickness was measured. The film thickness in this evaluation was measured using F20 made from FILMETRICS. MEA resistance (circle) and the thing which reduced the film thickness after postbaking, and the film thickness change after MEA treatment and drying were made into x.

[Evaluation results]

The results of the above evaluation are shown in Table 5 below.

Membrane Reduction ^* (μm) Resolution (μm) MEA immunity Example 11 none 0.25 ○ Example 12 none 0.25 ○ Example 13 none 0.25 ○ Comparative Example 6 none - × Comparative Example 7 none - × Comparative Example 8 disappearance - × Comparative Example 9 0.2 - ○

Initial film thickness: 0.5 μm

* "No film reduction" means that no film reduction was observed in the measurement results.

As can be seen from the results shown in Table 5, in Examples 11 to 13, all were high resolution, and the film reduction in the unexposed part was not seen, and had excellent MEA resistance.

On the contrary, in Comparative Examples 6 and 7, the pattern forming film reflowed at 230 ° C. for 30 minutes, and a mask dimension pattern could not be obtained. In addition, the film | membrane in which the pattern was not formed also reduced in film | membrane after MEA treatment after 230 degreeC and 30 minute post-baking. The film thickness after the MEA treatment was reduced by about 25% from the film thickness before the MEA treatment.

In Comparative Example 8, the film dissolved and disappeared due to development.

In addition, in the comparative example 9, the film | membrane reduction amount in the unexposed part at the time of image development is 0.2 micrometer, and the exposed part did not melt | dissolve completely and did not form a pattern.

[Preparation and Performance Test of Forged Photosensitive Resin Composition: 3]

<Examples 14 to 18>

According to the composition shown in following Table 6, in the specific copolymer solution (P1) obtained by carrying out similarly to the synthesis example 1 by the solution of (A) component, (B) component, (C) component, (D) component, and ( The positive photosensitive resin composition of each Example was prepared by mixing E) a solvent and (H) component in a predetermined ratio, stirring at 35 degreeC for 3 days, and making it a uniform solution.

Example 19

According to the composition similar to Example 16 shown in following Table 6, to the specific polymer solution (P1) obtained by carrying out similarly to the synthesis example 1 with the solution of (A) component, (B) component, (C) component, (D) A positive photosensitive resin composition was prepared by mixing a component, (E) solvent, and (H) component in a predetermined ratio, and stirring at 60 degreeC for 3 hours to make a uniform solution.

Example 20

According to the composition similar to Example 16 shown in following Table 6, to the specific polymer solution (P1) obtained by carrying out similarly to the synthesis example 1 with the solution of (A) component, (B) component, (C) component, (D The positive photosensitive resin composition was prepared by mixing the ()) component, the (E) solvent, and (H) component in a predetermined ratio, and stirring at 50 ° C for 3 hours to form a uniform solution.

Example 21

According to the composition similar to Example 16 shown in following Table 6, to the specific polymer solution (P1) obtained by carrying out similarly to the synthesis example 1 with the solution of (A) component, (B) component, (C) component, (D) A positive photosensitive resin composition was prepared by mixing a component, (E) solvent, and (H) component in a predetermined ratio, and stirring at 50 degreeC for 9 hours to make a uniform solution.

<Comparative Examples 10 to 13>

According to the composition shown in following Table 6, in the specific polymer solution (P1, P5, and P6) obtained by carrying out similarly to the synthesis example mentioned above with the solution of (A) component, (B) component, (C) component, (D The positive photosensitive resin composition of each comparative example was prepared by mixing a) component, (E) solvent, and (H) component in a predetermined ratio, and stirring at room temperature for 3 hours to make a uniform solution.

Solution (g) of component (A) (B) Component (g) (C) component (g) (D) component (g) (E) Solvent (g) (H) component (g) Example 14 P1 15 PVE1 0.83 NCO1 0.41 PAG1 0.21 PGMEA 5.75 R30 0.0028 Example 15 P1 15 PVE1 0.42 NCO1 0.41 PAG1 0.21 PGMEA 4.07 R30 0.0026 Example 16 P1 15 PVE1 0.21 NCO1 0.41 PAG1 0.21 PGMEA 3.23 R30 0.0025 Example 17 P1 15 PVE1 0.21 NCO1 0.41 PAG1 0.17 PGMEA 3.1 R30 0.0025 Example 18 P1 15 PVE1 0.21 NCO1 0.41 PAG1 0.13 PGMEA 3.0 R30 0.0025 Example 19 P1 15 PVE1 0.21 NCO1 0.41 PAG1 0.21 PGMEA 3.23 R30 0.0025 Example 20 P1 15 PVE1 0.21 NCO1 0.41 PAG1 0.21 PGMEA 3.23 R30 0.0025 Example 21 P1 15 PVE1 0.21 NCO1 0.41 PAG1 0.21 PGMEA 3.23 R30 0.0025 Comparative Example 10 P5 23.9 PVE1 1.11 NCO1 0.55 PAG1 0.28 PGME / PGMEA 0.57 / 3.3 R30 0.0037 Comparative Example 11 P6 19.6 PVE1 1.11 NCO1 0.55 PAG1 0.28 PGMEA 3.3 R30 0.0037 Comparative Example 12 P1 20 PVE1 1.11 - PAG1 0.28 PGME 1.6 R30 0.0034 Comparative Example 13 P1 20 - NCO1 0.55 PAG1 0.28 PGMEA 0.3 R30 0.0032

Comparative Example 14

Instead of the solution of the component (A), 20 g of the specific copolymer solution (P1) obtained in Synthesis Example 1 was used to substitute 1.1 g of the 1,2-quinonediazido compound of the component (C) and 1.1 g of the component (B). 1.1 g of GT4 as an epoxy-based crosslinkable compound, 0.0039 g of R30 as a surfactant of component (G), 0.25 g of MPTS as an adhesion aid, and 10.6 g of PGMEA as a solvent, and the mixture was stirred at room temperature for 8 hours. The positive photosensitive resin composition of the comparative example 14 was prepared by setting it as a uniform solution.

For each of the positive photosensitive resin compositions of Examples 14 to 21 and Comparative Examples 10 to 14 obtained, the sensitivity, the film reduction (in the unexposed portion), the light transmittance (transparency) after the high temperature baking, the light transmittance after the MEA treatment, and the MEA resistance, respectively And about each term of dimensional precision, it evaluated in the following procedure.

In addition, when obtaining a cured film from a positive photosensitive resin composition, in the comparative example 14, photo-bleaching deteriorates after the post-baking stage after image development, About Examples 14-21 and Comparative Examples 10-13, this photo After exposure, post-exposure heating (PEB) is performed at the pre-development stage without exposure, and in this respect, the evaluation procedures of both are different as follows.

[Evaluation of sensitivity]

<Examples 14-21, Comparative Examples 10-13>

After the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, prebaking was performed on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. The film thickness was measured using F20 made from FILMETRICS. The coating film was irradiated with ultraviolet light having a light intensity of 5.5 mW / cm ² at 365 nm for a certain period of time by a Canon ultraviolet irradiation device PLA-600FA, followed by post-exposure heating (PEB) on a hot plate at a temperature of 110 ° C. for 120 seconds. It was. After developing for 60 seconds by immersing in 0.4 mass% of TMAH aqueous solution for 60 second, it flow-washed with ultrapure water for 20 second. The minimum exposure amount (mJ / cm <^2> ) by which the debris melt | dissolved in the exposure part was made into the sensitivity.

Comparative Example 14

After the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, prebaking was performed on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. The film thickness was measured using F20 made from FILMETRICS. This coating film was irradiated with the ultraviolet-ray of 5.5 mW / cm <^2> for fixed time by the Canon ultraviolet irradiation device PLA-600FA at 365 nm. After developing for 60 seconds by immersing in 0.4 mass% of TMAH aqueous solution for 60 second, it flow-washed with ultrapure water for 20 second. The minimum exposure amount (mJ / cm <^2> ) by which the debris melt | dissolved in the exposure part was made into sensitivity.

[Evaluation of Membrane Reduction]

After the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, prebaking was performed on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. This film was immersed in 0.4 mass% of TMAH aqueous solution for 60 second, and the water was washed with ultrapure water for 20 second. Next, the film reduction degree of the unexposed part by the development was evaluated by measuring the thickness of this film. The film thickness in this evaluation was measured using F20 made from FILMETRICS.

[Evaluation of Light Transmittance (Transparency) after High Temperature Firing]

<Examples 14-21, Comparative Examples 10-13>

The positive photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. This coating film was immersed in 0.4 mass% of TMAH aqueous solution for 60 second, and it washed with water for 20 seconds with ultrapure water. Next, it post-baked by heating at 230 degreeC for 30 minutes, and the cured film with a film thickness of 1.9 micrometers was formed. The transmittance | permeability of 400 nm wavelength was measured for this cured film using the ultraviolet-visible spectrophotometer (The SIMADSU UV-2550 model number by Shimadzu Corporation). And after heating this coating film at 250 degreeC for 30 minutes, the transmittance | permeability of 400 nm wavelength was measured. The film thickness in this evaluation was measured using F20 made from FILMETRICS.

Comparative Example 14

The positive photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 2.4 μm. This coating film was immersed in 0.4 mass% of TMAH aqueous solution for 60 second, and it washed with water for 20 seconds with ultrapure water. The ultraviolet-ray irradiator PLA-600FA made by Canon irradiates the ultraviolet-ray of 5.5mW / cm <^2> at 800mJ to 800mJ / cm <^2> (photo-bleaching), and heats it at 230 degreeC for 30 minutes by the Canon ultraviolet irradiation device PLA-600FA. It post-baked and the cured film with a film thickness of 1.9 micrometers was formed. The transmittance | permeability of 400 nm wavelength was measured for this cured film using the ultraviolet perspective spectrophotometer (The SIMADSU UV-2550 model number by Shimadzu Corporation). And after heating this coating film at 250 degreeC for 30 minutes, the transmittance | permeability of 400 nm wavelength was measured. The film thickness in this evaluation was measured using F20 made from FILMETRICS.

[Evaluation of Light Transmittance and MEA Resistance after MEA Treatment]

<Examples 14-21, Comparative Examples 10-13>

The positive photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. This coating film was immersed in 0.4 mass% of TMAH aqueous solution for 60 second, and it washed with water for 20 seconds with ultrapure water. Next, it post-baked by heating at 230 degreeC for 30 minutes, and the cured film with a film thickness of 1.9 micrometers was formed. This coating film was immersed in monoethanolamine heated to 60 degreeC for 20 minutes, and it washed with pure water for 20 second. And after drying on a hotplate for 10 minutes at the temperature of 180 degreeC, the transmittance | permeability of 400 nm wavelength was measured using the film thickness measurement and the ultraviolet-visible spectrophotometer (Model SIMADSU UV-2550 by Shimadzu Corporation). The film thickness in this evaluation was measured using F20 made from FILMETRICS. MEA resistance (circle) and the thing which reduced the film thickness after postbaking, and the film thickness change after MEA treatment and drying were made into x.

Comparative Example 14

The positive photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 2.4 μm. This coating film was immersed in 0.4 mass% of TMAH aqueous solution for 60 second, and it washed with water for 20 seconds with ultrapure water. The coating film was irradiated with ultraviolet light having a light intensity of 5.5 mW / cm ² at 800 mJ / cm ² (photo-bleaching) at 365 nm by Canon ultraviolet irradiation device PLA-600FA, followed by heating at 230 ° C. for 30 minutes. It post-baked and the cured film with a film thickness of 1.9 micrometers was formed. This coating film was immersed in monoethanolamine heated to 60 degreeC for 20 minutes, and it washed with pure water for 20 second. And after drying on a hotplate for 10 minutes at the temperature of 180 degreeC, the transmittance | permeability of 400 nm wavelength was measured using the film thickness measurement and the ultraviolet-visible spectrophotometer (Model SIMADSU UV-2550 by Shimadzu Corporation). The film thickness in this evaluation was measured using F20 made from FILMETRICS. MEA resistance (circle) and the thing which reduced the film thickness after postbaking, and the film thickness after MEA treatment and drying were made into x.

[Dimension Accuracy]

<Examples 14-21, Comparative Examples 10-13>

After the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, prebaking was performed on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. The film thickness was measured using F20 made from FILMETRICS. Canon PLA-600FA the ultraviolet irradiation apparatus is the light intensity at 365nm 5.5mW / 40mJ / cm ² of ultraviolet light of ² cm in the parameter mask for line and space pattern of 8㎛ by irradiation to the coated film, and then the temperature 110 ℃ Post-exposure heating (PEB) was performed on a hot plate for 120 seconds at. Subsequently, after developing by immersing in 0.4 mass% of TMAH aqueous solution for 60 second, it flow-washed with ultrapure water for 20 second. Then, post-baking was performed on the hotplate for 30 minutes at 230 degreeC. The cross section of the formed pattern was observed using a scanning electron microscope (hereinafter referred to as SEM) to measure the line width. (Circle) that the pattern width is 8 micrometers, and the thing which does not hold | maintain 8 micrometers by expanding or contracting the pattern width was made into x.

Comparative Example 14

After the positive photosensitive resin composition was applied onto a silicon wafer using a spin coater, prebaking was performed on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. The film thickness was measured using F20 made from FILMETRICS. This coating film was irradiated with 200 mJ / cm <^2> of ultraviolet-rays with a light intensity of 5.5 mW / cm <^2> at 365 nm through the mask of a line-and-space pattern of 8 micrometers by Canon ultraviolet irradiation device PLA-600FA. Subsequently, after developing by immersing in 0.4 mass% of TMAH aqueous solution for 60 second, it flow-washed with ultrapure water for 20 second. Then, post-baking was performed on the hotplate for 30 minutes at 230 degreeC. The cross section of the formed pattern was observed using SEM and the line width was measured. (Circle) that the pattern width is 8 micrometers, and the thing which does not hold | maintain 8 micrometers by expanding or contracting the pattern width was made into x.

[Evaluation results]

The results of the above evaluation are shown in Table 7 below.

1 is a diagram showing the film thickness (μm, the film thickness remaining after melting in the exposed portion) with respect to the irradiation dose (mJ / cm ² ) in Examples 15, 16 and Comparative Example 14 (DNQ system). Indicates.

Sensitivity (mJ / cm ² ) Membrane Reduction ^* (μm) Transmittance (%) MEA immunity Dimensional precision 230 ℃ / 30 minutes 250 ° C / 30 minutes After MEA treatment Example 14 18 none 92 92 92 ○ ○ Example 15 15 none 87 88 88 ○ ○ Example 16 9 none 78 81 80 ○ ○ Example 17 12 none 78 81 80 ○ ○ Example 18 13 none 78 81 80 ○ ○ Example 19 19 none 80 80 80 ○ ○ Example 20 19 none 80 80 80 ○ ○ Example 21 19 none 80 80 80 ○ ○ Comparative Example 10 23 none 90 90 90 × × Comparative Example 11 23 none 91 91 91 × × Comparative Example 12 23 none 90 90 90 × × Comparative Example 13 23 disappearance - - - × × Comparative Example 14 80 0.2 92 85 86 ○ ○

* `` No film reduction '' means that no film reduction was observed in the measurement results.

As can be seen from the results shown in Table 7, in Examples 14 to 21, all of them were highly sensitive, and no film reduction in the unexposed part was observed, and the light transmittance was lowered even after high-temperature baking at 250 ° C (or 230 ° C) for 30 minutes. It was small, high transparency was maintained, and further, even after MEA treatment, there was little fall in transmittance, and it had the outstanding MEA tolerance and dimensional precision.

Moreover, the result shown in FIG. 1 showed that the sensitivity in Example 15 and Example 16 was improved significantly compared with the conventional naphthoquinone diazido (DNQ) system (comparative example 14).

On the contrary, in Comparative Examples 10-12, the pattern formation film was reflowed by 230 degreeC and 30 minute postbaking, and the desired shape and dimension pattern could not be obtained. In addition, the film | membrane in which the pattern was not formed also reduced by the MEA process after 230 degreeC and 30 minute post-baking. The film thickness after the MEA treatment was reduced by about 25% from the film thickness before the MEA treatment. In addition, the "transmittance after MEA process" of Table 7 is a value with respect to the film | membrane which the film | membrane reduction after MEA process generate | occur | produced.

In Comparative Example 13, the film dissolved and disappeared due to development.

And in the comparative example 14, the film reduction amount in the unexposed part at the time of image development was 0.2 micrometer. After 230 ° C. and 30 minutes of post-baking, the membrane's transmittance was 92%, but when baked at 250 ° C. for 30 minutes, the membrane's transmittance decreased to 85%. In addition, after MEA treatment after 230 degreeC and 30 minute post-baking, the transmittance | permeability of a film | membrane fell from 92% to 86%.

According to the present invention, it is possible to thermally crosslink between a compound having a vinyl ether group and to form a positive photosensitive resin composition having a composition capable of thermally curing a film between a compound having a block isocyanate group. The film is sufficiently sensitive and has a very small film reduction during development, and maintains a high transmittance even after firing at a high temperature such as 250 ° C. (or, for example, long time firing at 230 ° C.) after film formation. In addition, even when exposed to the resist stripping liquid (amine solution) treatment, it is possible to obtain the effect that the decrease in the film thickness and the decrease in the transmittance do not occur.

And according to this invention, when pattern formation is performed using the said positive photosensitive resin composition, the pattern (fine pattern size) of the outstanding resolution can be obtained.

Moreover, according to this invention, by obtaining a cured film using such a positive photosensitive resin composition, high transparency is maintained without a fall in transmittance even by high temperature (250 degreeC) baking or a resist stripping liquid (amine-type solution) process, It becomes a cured film excellent in heat resistance and chemical-resistance, and by this, uses of various film | membrane materials in liquid crystal or organic electroluminescent display, such as an array planarization film of TFT type liquid crystal element to which the chemically amplified resist was not applied conventionally, and micro The effect that it is suitable also for uses, such as a lens, can be acquired.

Furthermore, according to the production method of the present invention, it has a composition capable of thermal crosslinking with a compound having a vinyl ether group and thermal curing of the film between a compound having a block isocyanate group, and an alkali-soluble resin and a vinyl ether. A positive photosensitive resin composition containing a crosslinked product with a compound having a group to some extent can be obtained, and this composition is, of course, compared with a conventional method using a naphthoquinone diazido compound or the like, and a positive photosensitive type containing no crosslinked product. Even if compared with the resin composition, while achieving a sensitivity improvement, the film reduction of the unexposed part at the time of development is very small, and even after firing at a high temperature such as, for example, 250 ° C after the film formation (or, for example, 230 High transmittance is maintained even when firing at a temperature for a long time) and furthermore, it is not necessary to process a resist stripping liquid (amine solution). Even if the film does not occur the reduction of the thickness and the lowering of the transmission factor.

By the manufacturing method of this invention, it is suitable also for the use of various film | membrane materials in liquid crystal or organic electroluminescent display, such as an array planarization film | membrane of TFT type liquid crystal element to which the chemically amplified resist was not applied conventionally, and the use of a micro lens, etc. The manufacture of the positive photosensitive resin composition which can provide a cured film becomes very advantageous.

The positive photosensitive resin composition according to the present invention is suitable as a material for forming a cured film such as a protective film, a planarization film, and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display device, an organic EL device, and particularly, a TFT. It is also suitable as a material for forming an interlayer insulating film of a type liquid crystal device, a protective film of a color filter, an array planarizing film, an uneven film under the reflective film of a reflective display, an insulating film of an organic EL device, and the like, and also as various electronic materials such as micro lens materials. Suitable.

Claims (25)

A positive photosensitive resin composition containing following (A) component, (B) component, (C) component, (D) component, and (E) solvent. (A) component: It has a functional group for the thermal crosslinking reaction with the compound of (B) component, and a functional group for film | membrane hardening which can achieve the thermosetting reaction between the compound of (C) component, Further, alkali-soluble resins having a number average molecular weight of 2,000 to 30,000 (B) component: the compound which has 2 or more vinyl ether groups in 1 molecule (C) component: the compound which has a 2 or more block isocyanate group in 1 molecule (D) Component: photoacid generator (E) solvent The method of claim 1, The functional group for the thermal crosslinking reaction is at least one selected from the group of carboxyl groups and phenolic hydroxy groups, and the functional group for film curing is selected from the group of hydroxy groups other than phenolic hydroxy groups and amino groups having active hydrogens. At least 1 type is a positive type photosensitive resin composition. The method of claim 1, The (F) component further contains alkali-soluble resin other than the said (A) component, The positive photosensitive resin composition characterized by the above-mentioned. The method according to claim 1 or 2, Based on 100 mass parts of said (A) component, what contains 1-80 mass parts of said (B) components, 1-80 mass parts of said (C) components, and 0.5-80 mass parts of said (D) components A positive photosensitive resin composition characterized by the above-mentioned. The method of claim 4, wherein A positive photosensitive resin composition as (G) component which contains 0.001-5 mass parts of amine compounds further based on 100 mass parts of said (A) component. The method of claim 5, The (F) component further contains alkali-soluble resin other than the said (A) component, The positive photosensitive resin composition characterized by the above-mentioned. The method according to any one of claims 1 to 3, (H) As a component, surfactant is further contained 0.2 mass% or less in a positive photosensitive resin composition, The positive photosensitive resin composition characterized by the above-mentioned. The method of claim 5, (H) As a component, surfactant is further contained 0.2 mass% or less in a positive photosensitive resin composition, The positive photosensitive resin composition characterized by the above-mentioned. The process of apply | coating the positive photosensitive resin composition of any one of Claims 1-8 to a semiconductor substrate, The process of irradiating an ultraviolet-ray to the said application surface through a pattern mask, The said application surface is developed, and a pattern is developed on a semiconductor substrate. And a step of performing post-baking for film curing on the pattern forming surface. The method of claim 9, The said ultraviolet-ray is light which has at least 1 sort (s) of wavelength among i line | wire, g line | wire, and h line | wire. The method of claim 9, And the ultraviolet light is ArF, KrF or F ₂ laser light. The following thermal crosslinking reaction is carried out by mixing the following (A) component, (B) component, (C) component, (D) component, and (E) solvent, and keeping this mixed solution for a required period at temperature higher than room temperature. Proceeding to some extent, in addition to (A) component-(D) component, the positive photosensitive resin composition containing the crosslinked body of (A) component and (B) component is manufactured, The positive photosensitive resin composition of the Manufacturing method. (A) component: It has a functional group for the thermal crosslinking reaction with the compound of (B) component, and a functional group for film | membrane hardening which can achieve the thermosetting reaction between the compound of (C) component, Further, alkali-soluble resins having a number average molecular weight of 2,000 to 30,000 (B) component: the compound which has 2 or more vinyl ether groups in 1 molecule (C) component: the compound which has a 2 or more block isocyanate group in 1 molecule (D) Component: photoacid generator (E) solvent The method of claim 12, The mixed solution is maintained at a temperature of 30 to 70 ℃ for 2 hours to 5 days, the method for producing a positive photosensitive resin composition. The method according to claim 12 or 13, The functional group for thermal crosslinking reaction in the said (A) component is at least 1 sort (s) chosen from the group of a carboxyl group and a phenolic hydroxyl group, and the functional group for said film curing has hydroxyl groups other than a phenolic hydroxyl group, and active hydrogen It is at least 1 sort (s) chosen from the group of amino groups, The manufacturing method of the positive photosensitive resin composition characterized by the above-mentioned. The method of claim 12, The manufacturing method of the positive photosensitive resin composition characterized by further containing alkali-soluble resin other than the said (A) component as (F) component. The method according to claim 12 or 13, Based on 100 mass parts of said (A) component, 1-80 mass parts of said (B) components, 1-80 mass parts of said (C) component, and 0.5-80 mass parts of said (D) component are contained, It is characterized by the above-mentioned. The manufacturing method of the positive photosensitive resin composition made. The method of claim 16, (G) As a component, 0.001-5 mass parts of amine compounds are further contained based on 100 mass parts of said (A) component, The manufacturing method of the positive photosensitive resin composition characterized by the above-mentioned. The method of claim 17, The manufacturing method of the positive photosensitive resin composition characterized by further containing alkali-soluble resin other than the said (A) component as (F) component. The method according to claim 12, 13 or 15, (H) As a component, 0.2 mass% or less of surfactant is further contained in positive photosensitive resin composition, The manufacturing method of the positive photosensitive resin composition characterized by the above-mentioned. The method of claim 17, (H) As a component, 0.2 mass% or less of surfactant is further contained in positive photosensitive resin composition, The manufacturing method of the positive photosensitive resin composition characterized by the above-mentioned. The cured film obtained using the positive photosensitive resin composition of any one of Claims 1-8, or the positive photosensitive resin composition manufactured by the method of any one of Claims 12-20. The liquid crystal display element which has a cured film of Claim 21. The array planarizing film for liquid crystal displays which consists of a cured film of Claim 21. An interlayer insulating film made of the cured film according to claim 21. The micro lens which consists of a cured film of Claim 21.

Images