KR102203303B1 - Negative-type photosensitive composition curable at low temperature - Google Patents

Abstract

[Task] Providing a negative-type photosensitive composition capable of low-temperature curing and obtaining a cured film having high transparency and chemical resistance, and a pattern forming method using the same.
[Solution means] A negative photosensitive composition comprising a polysiloxane, a (meth)acrylic polymer, a compound containing two or more (meth)acryloyl groups, a polymerization initiator, and a solvent.

Description

Negative photosensitive composition capable of low temperature curing {NEGATIVE-TYPE PHOTOSENSITIVE COMPOSITION CURABLE AT LOW TEMPERATURE}

The present invention relates to a negative photosensitive composition. Further, the present invention relates to a method for producing a cured film using the same, a cured film formed therefrom, and a device having the cured film.

In recent years, in optical elements such as displays, light emitting diodes, and solar cells, various proposals have been made for the purpose of improving light utilization efficiency and saving energy. For example, in a liquid crystal display, a method of increasing the aperture ratio of a display device by forming a transparent planarization film over a thin film transistor (hereinafter, sometimes referred to as TFT) element and forming a pixel electrode on the planarization film is known ( See Patent Document 1).

Such a flat film can be formed by condensing a compound having a silanol group such as polysiloxane. In general, it is necessary to heat at a high temperature of 150°C or higher in order to rapidly advance the condensation reaction of the silanol group. In order to reduce the manufacturing cost, it is preferable that the heating temperature is low, so if you try to increase the reactivity of the silanol group to lower this heating temperature, the storage stability of the compound containing the silanol group or the composition containing the same may be impaired. many. For this reason, it has not been found that a composition capable of achieving both the possibility of low-temperature curing and composition stability has been found.

Japanese Patent Publication No. 2933879 Japanese Republished Patent Publication No. 2006-073021 Japanese Patent Laid-Open Publication No. 2011-190333

The present invention has been made on the basis of the above circumstances, and an object thereof is to provide a negative photosensitive composition capable of forming a cured film or pattern excellent in transparency, chemical resistance, and environmental resistance at a low temperature.

The negative photosensitive composition according to the present invention is characterized by containing a polysiloxane, a (meth)acrylic polymer, a compound containing two or more (meth)acryloyl groups, a polymerization initiator, and a solvent.

The method for producing a cured film according to the present invention includes applying the negative photosensitive composition to a substrate to form a coating film, and exposing the coating film to develop.

In addition, the cured film according to the present invention is characterized in that it is formed of the negative photosensitive composition.

In addition, the device according to the present invention is characterized in that it comprises the cured film.

The negative photosensitive composition of the present invention has high optical transparency, and is capable of forming a pattern or cured film having high chemical resistance and environmental resistance, and is also excellent in stability over time of the composition. In addition, since it can be cured in a low-temperature region, it is possible to manufacture a cured film or pattern at lower cost without requiring a heating process after exposure. In addition, since the obtained cured film is excellent in flatness and electrical insulation properties, including a planarization film for a thin film transistor (TFT) substrate used for a backplane of displays such as a liquid crystal display device or an organic EL display device, or an interlayer insulating film of a semiconductor device, It can be suitably used as various film-forming materials such as insulating films or transparent protective films in solid-state imaging devices, antireflection films, antireflection plates, optical filters, high-brightness light emitting diodes, touch panels, solar cells, etc., or optical elements such as optical waveguides. have.

Negative photosensitive composition

The negative photosensitive composition according to the present invention is characterized by containing at least a polysiloxane, a (meth)acrylic polymer, a compound containing two or more (meth)acryloyl groups, a polymerization initiator, and a solvent. Hereinafter, each component used in the negative photosensitive composition of the present invention will be sequentially described in detail.

(I) polysiloxane

The composition according to the present invention contains polysiloxane as a main component. Although polysiloxane refers to a polymer containing a Si-O-Si bond, in the present invention, in addition to an unsubstituted inorganic polysiloxane, an organic polysiloxane substituted with an organic group substituent is also referred to as a polysiloxane. These polysiloxanes generally have a silanol group or an alkoxysilyl group. These silanol groups and alkoxysilyl groups mean a hydroxyl group and an alkoxy group directly bonded to silicon forming a siloxane skeleton. Here, the silanol group and the alkoxysilyl group are considered to have an effect of accelerating the curing reaction when forming a cured film using the composition, and also contribute to a reaction with a silicon-containing compound described later. For this reason, it is preferable that the polysiloxane has these groups.

The structure of the polysiloxane used in the present invention is not particularly limited, and may be selected from arbitrary ones depending on the purpose. The skeleton structure of the polysiloxane is a silicon skeleton (the number of oxygen atoms bonded to the silicon atom is 2), the silsesquioxane skeleton (the number of oxygen atoms bonded to the silicon atom is 3), and silica, depending on the number of oxygen bonded to the silicon atom. It can be classified into a skeleton (the number of oxygen atoms bonded to a silicon atom is 4). In the present invention, any of these may be used. The polysiloxane molecule may contain a plurality of combinations of such skeletal structures.

In addition, in the case of using an organic polysiloxane, the substituents contained therein can be selected from any ones as long as the effect of the present invention is not impaired. Examples of such substituents include substituents that do not contain Si-O bonds constituting the siloxane structure, specifically an alkyl group, a hydroxyalkyl group, and an aryl group, and a group in which the hydrogen atom of these groups is substituted with an unsaturated hydrocarbon group.

In addition, as long as the effect of the present invention is not impaired, reactive groups other than silanol groups or alkoxysilyl groups, such as carboxyl groups, sulfonyl groups, amino groups, etc., may be contained in the siloxane resin, but these reactive groups are generally applied to the composition. Since there is a tendency to deteriorate the storage stability of, less is preferable. Specifically, it is preferably 10 mol% or less with respect to the total number of hydrogens or substituents bonded to the silicon atom, and particularly preferably not contained at all.

In addition, the composition according to the present invention is for forming a cured film on a substrate by application, pattern exposure, and development. For this reason, it is necessary to generate a difference in solubility in the exposed portion and the unexposed portion. In the present invention, a curing reaction occurs in the exposed portion and becomes insoluble in a developer, thereby forming an image. Therefore, the polysiloxane in the unexposed portion must have a certain or higher solubility in the developer. For example, if the dissolution rate in the 2.38% tetramethylammonium hydroxide (hereinafter sometimes referred to as TMAH) aqueous solution of the film to be formed is 50 Å/sec or more, it is considered that the formation of a negative pattern by exposure-phenomena is possible. . However, since the solubility required is different depending on the film thickness or development conditions of the formed film, it is necessary to appropriately select a polysiloxane according to the development conditions.

However, simply selecting a polysiloxane having a high dissolution rate may cause problems such as deformation of the pattern shape, decrease in film residual rate, and decrease in transmittance. In order to improve this problem, a polysiloxane mixture incorporating a polysiloxane having a slow dissolution rate can be used.

Such polysiloxane mixtures, for example

(Ia) a first polysiloxane in which the film after prebaking is soluble in a 5% by weight aqueous solution of tetramethylammonium hydroxide and its dissolution rate is 3,000 Å/sec or less,

(Ib) Polysiloxane having a dissolution rate of 150 Å/sec or more in a 2.38 wt% tetramethylammonium hydroxide aqueous solution of the film after prebaking

It contains. These polysiloxanes will be described.

(a) first polysiloxane

The first polysiloxane (Ia) is a polysiloxane in which the film after prebaking is soluble in a 5% by weight aqueous solution of tetramethylammonium hydroxide and its dissolution rate is generally 3,000 Å/sec or less, preferably 2,000 Å/sec or less. It is poorly soluble in 2.38% TMAH aqueous solution.

The first polysiloxane can be obtained by hydrolyzing and condensing a silane compound (ia) selected from the group consisting of trialkoxysilane and tetraalkoxysilane in the presence of a basic catalyst.

As the silane compound (ia) selected from the group consisting of trialkoxysilane and tetraalkoxysilane used as a raw material, any one may be used, but for example, one represented by the following formula (i) may be used.

Formula i

R ¹ _n Si(OR ₂ ) _4-n

In Formula i,

R ¹ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms in which any methylene may be substituted with oxygen, or an aryl group in which hydrogen may be substituted with fluorine having 6 to 20 carbon atoms,

n is 0 or 1,

R ² is an alkyl group having 1 to 5 carbon atoms.

In the formula (i), as R ¹ , for example, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2,2,2 -Trifluoroethyl group, 3,3,3-trifluoropropyl group, cyclohexyl group, phenyl group, and tolyl group. In particular, a compound in which R ¹ is a methyl group is preferable because it is easy to obtain raw materials, has high film hardness after curing, and has high chemical resistance. In addition, a phenyl group is preferable because the solubility of the polysiloxane in a solvent is increased and the cured film is less likely to crack.

On the other hand, in the general formula (i), examples of R ² include methyl group, ethyl group, n-propyl group, isopropyl group, and n-butyl group. In the formula (i), a plurality of R ² is contained, but each R ² may be the same or different.

Specific examples of the trialkoxysilane compound represented by Formula (i) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrin-butoxysilane, ethyltrimethoxysilane. , Ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltri Ethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoro Methyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc. are mentioned. Among these, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are readily available and are preferable compounds.

In addition, specific examples of the tetraalkoxysilane compound represented by the above formula (i) include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like. Among them, tetramethoxysilane Toxysilane, tetraethoxysilane, and the like are preferred because of their high reactivity.

The silane compound (ia) used in the production of the first polysiloxane (Ia) may be used alone or in combination of two or more. Here, when tetraalkoxysilane is used as the silane compound (ia), the pattern sag tends to be reduced. This is considered to be because the crosslinking density of polysiloxane increases. However, if the compounding ratio of tetraalkoxysilane is too large, there is a possibility that the sensitivity is lowered. For this reason, in the case of using tetraalkoxysilane as a raw material for polysiloxane (Ia), the blending ratio thereof is preferably 0.1 to 40 mol% with respect to the total number of moles of trialkoxysilane and tetraalkoxysilane, and 1 to 20 mol% It is more preferable that it is.

It is preferable that the polysiloxane (Ia) used in the present invention is produced by hydrolyzing and condensing the silane compound in the presence of a basic catalyst.

For example, a silane compound or a mixture of a silane compound is added dropwise to a reaction solvent consisting of an organic solvent, a basic catalyst, and water, followed by hydrolysis and condensation reaction, and purifying by neutralization or washing, and further concentration as necessary. Thereafter, if necessary, it can be produced by substituting the reaction solvent with a desired organic solvent.

Examples of the organic solvent used in the reaction solvent include hydrocarbon solvents such as hexane, toluene, xylene, and benzene, ether solvents such as diethyl ether and tetrahydrofuran, ethyl acetate, and propylene glycol monomethyl ethyl acetate. Ester solvents, alcohol solvents such as methanol, ethanol, isopropanol, butanol, and 1,3-dipropanol, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. These organic solvents may be used alone. Or it can be used in combination of a plurality. In addition, the amount of the organic solvent to be used is generally 0.1 to 10 times by weight, preferably 0.5 to 2 times by weight of the mixed liquid of the silane compound.

The reaction temperature for carrying out the hydrolysis and condensation reaction is generally 0 to 200°C, preferably 10 to 60°C. At this time, the temperature of the silane compound to be dropped and the temperature of the reaction solvent may be the same or different. The reaction time varies depending on the kind of the silane compound, etc., but it is usually several tens of minutes to several tens of hours, preferably 30 minutes or more. Various conditions in the hydrolysis and condensation reaction are physical properties suitable for the intended use by setting, for example, the amount of basic catalyst, reaction temperature, reaction time, etc., taking into account the reaction scale, the size, and shape of the reaction vessel. Can be obtained.

Examples of the basic catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, and alkoxysilane having an amino group. Organic bases, inorganic bases such as sodium hydroxide and potassium hydroxide; anion exchange resin; quaternary ammonium salts such as tetrabutylammonium hydroxide, tetraethylammonium hydroxide, and tetramethylammonium hydroxide. The amount of catalyst is preferably 0.0001 to 10 mole times of the mixture of the silane compound. Polysiloxane synthesized using such a basic catalyst has a feature that curing starts quickly when a temperature of 150° C. or higher is applied, and a clean shape can be maintained without causing pattern sag even after firing.

The degree of hydrolysis can be adjusted by the amount of water added to the reaction solvent. In general, it is preferable to react water in a ratio of 0.01 to 10 mole times, preferably 0.1 to 5 mole times, with respect to the hydrolyzable alkoxy group of the silane compound. If the added amount of water is too low than the above range, the degree of hydrolysis is lowered, making it difficult to form a film of the composition, which is not preferable. On the other hand, if the amount is too high, gelation is likely to occur and storage stability is deteriorated. In addition, the water used is preferably ion-exchanged water or distilled water.

After completion of the reaction, the reaction solution may be made neutral or weakly acidic using an acidic compound as a neutralizing agent. Examples of acidic compounds include inorganic acids such as phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, or hydrofluoric acid, and polyhydric carboxylic acids of acetic acid, trifluoroacetic acid, formic acid, lactic acid, acrylic acid, oxalic acid, maleic acid, succinic acid, or citric acid, and anhydrides thereof, and organic acids such as p-toluenesulfonic acid or sulfonic acid such as methanesulfonic acid. It can also be neutralized using a cation exchange resin.

The amount of the neutralizing agent is appropriately selected depending on the pH of the reaction solution after the reaction, but is preferably 0.5 to 1.5 mole times, more preferably 1 to 1.1 mole times, with respect to the basic catalyst. Moreover, when using a cation exchange resin, it is preferable to make the number of ionic groups contained in a cation exchange resin fall within the said range.

The reaction solution after neutralization may be washed and purified if necessary. The washing method is not particularly limited, for example, adding a hydrophobic organic solvent and water as necessary to the reaction solution after neutralization, stirring, and bringing the organic solvent into contact with the polysiloxane to dissolve at least polysiloxane (Ia) in a hydrophobic organic solvent. . At this time, as the hydrophobic organic solvent, a compound that dissolves polysiloxane (Ia) and is incompatible with water is used. Incompatible with water means that water and a hydrophobic organic solvent are sufficiently mixed and left to stand to separate into an aqueous phase and an organic phase.

Preferred hydrophobic organic solvents include ether solvents such as diethyl ether, ester solvents such as ethyl acetate, alcohol solvents poor in solubility in water such as butanol, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, And aromatic solvents such as toluene and xylene. The hydrophobic organic solvent used for washing may be the same as or different from the organic solvent used as the reaction solvent, and may be used in combination of two or more. By such washing, most of the basic catalyst used in the reaction process, the neutralizing agent, and the salt produced by the neutralization, as well as alcohol or water, which are by-products of the reaction, are contained in the aqueous layer and are substantially removed from the organic layer. The number of cleanings can be changed as needed.

The temperature at the time of washing is not particularly limited, but is preferably 0 to 70°C, more preferably 10 to 60°C. Further, the temperature at which the aqueous phase and the organic phase are separated is also not particularly limited, but is preferably 0 to 70°C, and from the viewpoint of shortening the liquid separation time, more preferably 10 to 60°C.

By performing such washing, the coating property and storage stability of the composition may be improved in some cases.

The reaction solution after washing may be added as it is to the composition according to the present invention, but if necessary, the concentration is changed by removing the solvent or alcohol or water, which is a by-product of the remaining reaction, by concentration, or the solvent is used as another solvent. It can also be substituted. In the case of performing concentration, it can be carried out under normal pressure (atmospheric pressure) or reduced pressure, and the degree of concentration can be arbitrarily changed by controlling the amount of outflow. The temperature at the time of concentration is generally 30 to 150°C, preferably 40 to 100°C. Further, the solvent may be substituted by adding a desired solvent at an appropriate time point and further concentrating to obtain the desired solvent composition.

The polysiloxane (Ia) used in the siloxane resin composition of the present invention can be produced by the above method.

(b) second polysiloxane

The second polysiloxane is a polysiloxane whose film after prebaking is soluble in a 2.38% by weight aqueous tetramethylammonium hydroxide solution and has a dissolution rate of 150 angstroms/second or more, preferably 300 angstroms/second or more.

This polysiloxane (Ib) can be produced by hydrolyzing and condensing a silane compound (ib) selected from the group consisting of trialkoxysilane and tetraalkoxysilane in the presence of an acidic or basic catalyst.

Here, as conditions of this manufacturing method, the same method as the manufacturing method of polysiloxane (Ia) can be used. However, as a reaction catalyst, an acidic catalyst can be used in addition to a basic catalyst. Further, in order to achieve the desired dissolution rate, conditions such as the amount of addition of the reaction solvent, particularly water, reaction time, and reaction temperature, are appropriately prepared.

The silane compound (ib) may be the same as or different from the silane compound (ia) used as a raw material for the polysiloxane (Ia). Here, when tetraalkoxysilane is used as the silane compound (ib), the pattern sag tends to be reduced.

Further, when a relatively large amount of tetraalkoxysilane is used as the raw material of the first polysiloxane (Ia), it is preferable that the blending ratio of the tetraalkoxysilane as the raw material of the second polysiloxane (Ib) is low. This is because when the compounding ratio of tetraalkoxysilane as a whole is high, precipitation of a silane compound occurs, or a decrease in sensitivity of the formed film occurs. For this reason, it is preferable that the blending ratio of tetraalkoxysilane is 1 to 40 mol%, and 1 to 20 mol% with respect to the total number of moles of the silane compounds (ia) and (ib), which are the raw materials of polysiloxanes (Ia) and (Ib). It is more preferable that it is %.

In addition, in the production of polysiloxane (Ib), an acidic catalyst can be used as a catalyst. Examples of the acidic catalyst that can be used include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyhydric carboxylic acid, or anhydrides thereof. The amount of the catalyst added is also different depending on the strength of the acid, but is preferably 0.0001 to 10 mole times of the mixture of the silane compound.

When an acidic catalyst is used for the production of polysiloxane (Ib), the reaction solution may be neutralized after completion of the reaction, as in the case of using a basic catalyst. In this case, a basic compound is used as a neutralizing agent. Examples of the basic compound used for neutralization include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, or diethanolamine, etc. Organic bases, inorganic bases such as sodium hydroxide or potassium hydroxide, quaternary ammonium salts such as tetrabutylammonium hydroxide, tetraethylammonium hydroxide, and tetramethylammonium hydroxide. Anion exchange resin can also be used. The amount of the neutralizing agent may be the same as in the case of using a basic catalyst. Although it is appropriately selected depending on the pH of the reaction solution after the reaction, it is preferably 0.5 to 1.5 mole times, more preferably 1 to 1.1 mole times with respect to the acidic catalyst.

By the above, the polysiloxane (Ib) used in the siloxane resin composition of the present invention can be produced.

The dissolution rate of the polysiloxane (Ib) in the 2.38% TMAH aqueous solution is required to be 150 Å/sec or more, and preferably 300 Å/sec or more, as described later. If the dissolution rate of the polysiloxane (Ib) in the 2.38% TMAH aqueous solution is less than 150 Å/sec, the dissolution rate of the mixture of the polysiloxane (Ia) and (Ib) in the 2.38% TMAH aqueous solution is 50 to 5,000 Å/sec. It is necessary to reduce the content of adult polysiloxane (Ia) as much as possible, but if the content of polysiloxane (Ia) is small, it becomes difficult to prevent thermal sagging of the pattern.

(c) polysiloxane mixture (I)

In the present invention, a polysiloxane mixture (I) containing the above polysiloxane (Ia) and polysiloxane (Ib) can be used. The blending ratio of the polysiloxane (Ia) and the polysiloxane (Ib) is not particularly limited, but the weight ratio of the polysiloxane (Ia) / polysiloxane (Ib) contained in the polysiloxane mixture (I) is preferably 1/99 to 80/20, and 20 It is more preferable that it is /80-50/50.

If the dissolution rate of polysiloxane (Ia) in 5% TMAH aqueous solution is 3,000 Å/sec or less, and the dissolution rate of polysiloxane (Ib) in 2.38% TMAH aqueous solution is 150 Å/sec or more, the problem remains without dissolution or sensitivity reduction Is not remarkable, but the dissolution rate of the polysiloxane mixture (I) in 2.38% TMAH aqueous solution may be appropriately set according to the film thickness or development time of the cured film formed from the negative photosensitive composition of the present invention. The dissolution rate of the polysiloxane mixture (I) can be adjusted by changing the mixing ratio of the polysiloxanes (Ia) and (Ib), and varies depending on the type or amount of the photosensitive agent contained in the negative photosensitive composition, but, for example, the film When the thickness is 0.1 to 10 µm (1,000 to 100,000 Å), the dissolution rate in the 2.38% TMAH aqueous solution is preferably 50 to 5,000 Å/sec.

Further, when using a polysiloxane mixture, the weight average molecular weight of the entire polysiloxane is preferably 5,000 or less, more preferably 4,000 or less. The same is true when a single polysiloxane is used instead of a polysiloxane mixture. Moreover, when using a polysiloxane mixture, it is preferable that the weight average molecular weight of each polysiloxane is 5,000 or less. In addition, in the present invention, the weight average molecular weight is a weight average molecular weight in terms of styrene obtained by gel permeation chromatography.

(d) Alkali dissolution rate in TMAH aqueous solution

In the present invention, the polysiloxanes (Ia) and (Ib) each have a specific dissolution rate for the TMAH aqueous solution. The dissolution rate of polysiloxane in the TMAH aqueous solution is measured as follows. Polysiloxane is diluted to 35% by weight in propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), and dissolved while stirring at room temperature with a stirrer for 1 hour. In a clean room under an atmosphere of 23.0±0.5°C and 50±5.0% humidity, the prepared polysiloxane solution was dropped onto the center of a 1cc silicon wafer using a pipette on a 4 inch, 525 μm thick silicon wafer. After spin coating to a thickness, the solvent is removed by heating on a hot plate at 100° C. for 90 seconds. The film thickness of the coating film is measured with a spectroscopic ellipsometer (manufactured by J.A. Woollam).

Next, the silicon wafer with this film was quietly immersed in a 6-inch-diameter glass chalet containing 100 ml of TMAH aqueous solution of a predetermined concentration, adjusted to 23.0±0.1°C, and allowed to stand, and the time until the film disappeared was measured. I did. The dissolution rate is obtained by dividing the time from the end of the wafer to the disappearance of the film in the 10 mm inner portion. If the dissolution rate is remarkably slow, the wafer is immersed in TMAH aqueous solution for a certain period of time and then heated on a hot plate at 200° C. for 5 minutes to remove moisture that entered the film during the dissolution rate measurement, and then the film thickness is measured before and after immersion The dissolution rate is calculated by dividing the amount of change in the thickness of the film by the immersion time. The above measurement was carried out 5 times, and the average of the obtained values was taken as the dissolution rate of the polysiloxane.

( II ) ( Met ) Acrylic polymer

The negative photosensitive composition according to the present invention contains a (meth)acrylic polymer. Here, the (meth)acrylic polymer is a generic term for a polymer obtained by polymerizing at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, acrylate and methacrylate. These polymers may be copolymers obtained by polymerizing different monomers, and may contain monomers other than those described above within a range that does not impair the effects of the present invention. As such (meth)acrylic polymer, any conventionally known one may be used, but in the present invention, from the viewpoint of reactivity, a (meth)acrylic polymer containing a repeating unit having an unsaturated bond, and a repeating unit having an acid group. It is preferable to use a (meth)acrylic polymer, and it is more preferable to use both of these.

As a (meth)acrylic polymer containing a repeating unit having an unsaturated bond, a vinyl group, acryloyl group, methacryloyl group, acetylenyl group, acid anhydride typified by maleic acid or itaconic acid, maleimide, etc. Acrylic polymers and methacrylic polymers having a group containing a carbon-carbon unsaturated bond, such as an anhydride of deacid, may be mentioned. These compounds react with other reactive components contained in the composition by their unsaturated bonds to form a crosslinked structure.

In addition, it is preferable that the (meth)acrylic polymer containing a repeating unit having an unsaturated bond has a silicon-containing group in order to improve the compatibility of the polysiloxane. Specifically, a (meth)acrylic polymer substituted with a siloxy group or a silanol group, a silane coupling agent having a carbon-carbon unsaturated bond, a silicone oligomer, or a (meth)acrylic polymer reacted with a silicone oil are preferred. A copolymer of a silicone coupling agent and a (meth)acrylic polymer is particularly preferred. Here, as a silicone coupling agent, KBM-1003, KME-1003, KBM-1403, and KMB-5103, as a silicone oligomer, X-40-9272B, KR-513, X-40-2672B, and X-40-9272B As the silicone oil, X-22-174DX, X-22-2426, X-22-2475, and X-22-1602 (any of which are brand names, manufactured by Shin-Etsu Chemical Industries, Ltd.) can be mentioned.

The weight average molecular weight of such a polymer is not particularly limited, but it is preferably 2,000 to 100,000, and more preferably 3,000 to 30,000. In addition, the number of unsaturated bonds is not particularly limited, but it is preferable that the double bond equivalent is 10 to 500 g/eq from the viewpoint of making reactivity and storage properties compatible.

Examples of the (meth)acrylic polymer containing a repeating unit having an acid group include an acrylic polymer or a methacrylic polymer having a carboxyl group, a sulfo group, a phenolic hydroxyl group, or the like in the side chain. When these polymers have an acidic group, the solubility of the uncured portion during development is promoted.

The weight average molecular weight of such a polymer is not particularly limited, but it is preferably 2,000 to 100,000, and more preferably 3,000 to 30,000. In addition, the number of acid groups is not particularly limited, but it is preferable that the acid value is 50 to 500 mgKOH/g from the viewpoint of making reactivity and storage properties compatible.

When a (meth)acrylic polymer containing a repeating unit having an unsaturated bond and a (meth)acrylic polymer containing a repeating unit having an acidic group are used in combination, the blending ratio is not particularly limited, but the uncured portion at the time of development It is preferably 8:2 to 2:8 from the viewpoint of ensuring the solubility of and making the reactivity at the time of curing compatible.

In addition, it is also preferable to use a (meth)acrylic polymer containing both a repeating unit having an unsaturated bond and a repeating unit having an acid group. Also in such a (meth)acrylic polymer, the number of unsaturated bonds and the number of acid groups are not particularly limited, but it is preferable that the double bond equivalent is 10 to 500 g/eqm and the acid value is 5 to 150 mgKOH/g.

In addition, the blending ratio of the polysiloxane and the (meth)acrylic polymer is not particularly limited, but it is preferable that the blending ratio of the (meth)acrylic polymer is high from the viewpoint of heat resistance and transparency after curing, while the blending ratio of polysiloxane from the viewpoint of chemical resistance after curing It is desirable to have many. For this reason, the blending ratio of the polysiloxane and the (meth)acrylic polymer is preferably 90:10 to 10:90, and more preferably 75:25 to 25:75.

( III ) ( Met ) Acryloyl group Compounds containing two or more

The negative photosensitive composition according to the present invention contains a compound containing two or more (meth)acryloyl groups (hereinafter sometimes referred to as a (meth)acryloyl group-containing compound for simplicity). Here, the (meth)acryloyl group is a generic term for an acryloyl group and a methacryloyl group. This compound is a compound capable of forming a crosslinked structure by reacting with the polysiloxane and the (meth)acrylic polymer. Here, in order to form a crosslinked structure, a compound containing two or more reactive groups such as acryloyl or methacryloyl groups is required, and three or more acryloyl groups or methacryloyl groups are required to form a higher-dimensional crosslinked structure. It is preferable to contain. As the compound containing two or more (meth)acryloyl groups, (α) a polyol compound having two or more hydroxyl groups and (β) esters obtained by reacting two or more (meth)acrylic acids are preferably used. As the polyol compound (α), a compound having as a basic skeleton a saturated or unsaturated aliphatic hydrocarbon, an aromatic hydrocarbon, a heterocyclic hydrocarbon, a primary, secondary, or tertiary amine, an ether, etc., and having two or more hydroxyl groups as substituents Can be lifted. The polyol compound may contain other substituents, such as a carboxyl group, a carbonyl group, an amino group, an ether bond, a thiol group, a thioether bond, and the like, as long as the effect of the present invention is not impaired. As a preferable polyol compound, alkyl polyol, aryl polyol, polyalkanol amine, cyanuric acid, dipentaerythritol, etc. are mentioned. Here, when the polyol compound (?) has three or more hydroxyl groups, it is not necessary for all hydroxyl groups to react with meta (acrylic acid), and may be partially esterified. That is, the esters may have unreacted hydroxyl groups. Examples of such esters include tris(2-acryloxyethyl)isocyanurate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, pentaerythritol tetra(meth)acrylate, Dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, polytetramethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, tricyclodecanedi Methanol diacrylate, 1,9-nonanediol diacrylate, 1,6-hexanediol diacrylate, 1,10-decanediol diacrylate, etc. are mentioned. Among these, tris(2-acryloxyethyl)isocyanurate and dipentaerythritol hexaacrylate are preferable from the viewpoint of the reactivity and the number of crosslinkable groups. Further, in order to adjust the shape of the pattern to be formed, two or more types of these compounds may be combined. Specifically, a compound containing three (meth)acryloyl groups and a compound containing two (meth)acryloyl groups can be combined.

It is preferable that such a compound is a molecule relatively smaller than that of a polymer from the viewpoint of reactivity. For this reason, it is preferable that the molecular weight is 2000 or less, and it is preferable that it is 1500 or less.

The blending amount of the acryloyl group-containing compound is adjusted according to the type of the polymer or acryloyl group-containing compound to be used, but from the viewpoint of compatibility with the resin, 3 parts by weight of the total weight of the polysiloxane and the (meth)acrylic polymer. It is preferably to 50 parts by weight. In addition, these acryloyl group-containing compounds may be used alone or in combination of two or more.

( IV ) Polymerization Initiator

The negative photosensitive composition according to the present invention contains a polymerization initiator. This polymerization initiator includes a polymerization initiator that generates an acid, a base or a radical by radiation, and a polymerization initiator that generates an acid, a base or a radical by heat.

The polymerization initiator can improve the resolution by strengthening the shape of the pattern or increasing the contrast of development. Examples of the polymerization initiator used in the present invention include a photoacid generator that decomposes upon irradiation with radiation and releases an acid, an active substance that photocures the composition, a photobase generator that releases a base, a photoradical generator that releases radicals, and And a thermal acid generator that releases an acid, which is an active substance that is decomposed by heat to heat-cure the composition, a hot base generator that releases a base, and a thermal radical generator that releases a radical. Here, examples of the radiation include visible light, ultraviolet rays, infrared rays, X-rays, electron beams, α rays or γ rays.

The amount of polymerization initiator to be added varies depending on the type and amount of active substances generated by decomposition of the polymerization initiator, and the required sensitivity and dissolution contrast of the exposed and unexposed regions, but the total weight of the polysiloxane and (meth)acrylic polymer. Based on 100 parts by weight, it is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight. When the addition amount is less than 0.001 parts by weight, the dissolution contrast between the exposed portion and the unexposed portion is too low, and the addition effect may not be obtained. On the other hand, when the addition amount of the polymerization initiator is more than 10 parts by weight, cracks may occur in the film to be formed, or the colorlessness and transparency of the film may be deteriorated in some cases because coloration due to decomposition of the polymerization initiator may be remarkable. In addition, when the amount of addition increases, thermal decomposition may cause deterioration of the electrical insulating properties of the cured product or release of gas, which may lead to a problem in a post process. In addition, the resistance of the coating film to a photoresist stripper containing monoethanolamine or the like as a main substance may decrease.

Examples of the photoacid generator include diazomethane compounds, diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, ammonium salts, phosphonium salts, and sulfonimide compounds. The structure of these photoacid generators can be represented by the formula (A).

Formula A

R ⁺ X ^-

Here, R ⁺ is an organic ion selected from the group consisting of hydrogen, an alkyl group modified with a carbon atom or other hetero atom, an aryl group, an alkenyl group, an acyl group, and an alkoxyl group, such as diphenyliodonium ion, triphenylsulfur Represents a phonium ion.

In addition, it is preferable that X ^- is any one of a pair ion represented by the following formula.

In the above formula,

Y is a halogen atom,

R ^a is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms substituted with a substituent selected from fluorine, nitro group, and cyano group,

R ^b is hydrogen or an alkyl group having 1 to 8 carbon atoms,

p is a number from 0 to 6,

q is a number from 0 to 4.

As a specific counter ion ^{_{BF 4 -, (C 6 F}} 5) 4 B -, ((CF 3) 2 C 6 H 3) 4 B -, PF 6 -, (CF 3 CF 2) 3 PF 3 -, SbF 6 ^{_{-, (C 6 F 5)}} 4 Ga -, ((CF 3) 2 C 6 H 3) 4 Ga -, SCN -, (CF 3 SO 2) 3 C -, (CF 3 SO 2) 2 N -, Consisting of formic acid ion, acetate ion, trifluoromethanesulfonic acid ion, nonafluorobutanesulfonic acid ion, methanesulfonic acid ion, butanesulfonic acid ion, benzenesulfonic acid ion, p-toluenesulfonic acid ion, and sulfonic acid ion Some are selected from the group.

Among the photoacid generators used in the present invention, it is particularly good to generate sulfonic acids or boric acids, and for example, tolylcumyliodonium tetrakis (pentafluorophenyl) boric acid (PHOTOINITIATOR 2074 manufactured by Rhodia (brand name)), Diphenyliodonium tetra (perfluorophenyl) boric acid, sulfonium ions in the cation portion and pentafluoroborate ions in the anion portion are mentioned. In addition, triphenylsulfonium trifluoromethanesulfonic acid, triphenylsulfonium campasulfonic acid, triphenylsulfonium tetra (perfluorophenyl) boric acid, 4-acetoxyphenyldimethylsulfonium hexafluorobic acid, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonic acid, 1-(4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethane Sulfonic acid, diphenyliodonium trifluoromethanesulfonic acid, diphenyliodonium hexafluorobiic acid, and the like. In addition, a photoacid generator represented by the following formula may also be used.

In the above formula,

A is each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylcarbonyl group having 1 to 20 carbon atoms, an arylcarbonyl group having 6 to 20 carbon atoms, a hydroxyl group, And a substituent selected from an amino group,

p is each independently an integer of 0 to 5,

B ⁻ includes a fluorinated alkyl sulfonate group, a fluorinated aryl sulfonate group, a fluorinated alkyl borate group, an alkyl sulfonate group, and an aryl sulfonate group. A compound obtained by exchanging cations and anions represented by these formulas, or a photoacid generator in which a cation or anion represented by these formulas and various cations or anions described above are combined may be used. For example, a combination of any one of the sulfonium ions represented by the formula and a tetra(perfluorophenyl)borate ion, and any one of the iodonium ions represented by the formula and a tetra(perfluorophenyl)borate ion. The combination can also be used as a photoacid generator.

Examples of the thermal acid generator include various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids such as citric acid, acetic acid and maleic acid and salts thereof, various aromatic carboxylic acids such as benzoic acid and phthalic acid and salts thereof, aromatic sulfonic acids and ammonium salts thereof, and various amine salts. , Aromatic diazonium salts, phosphonic acids and salts thereof, and salts and esters that generate organic acids. Among the thermal acid generators used in the present invention, in particular, a salt consisting of an organic acid and an organic base is preferable, and a salt consisting of a sulfonic acid and an organic base is more preferable.

Preferred thermal acid generators containing sulfonic acid include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, and the like. These acid generators can be used alone or in combination.

Examples of the photobase generator include polysubstituted amide compounds having an amide group, lactams, imide compounds, or those containing the structure.

Examples of the hot base generator include N-(2-nitrobenzyloxycarbonyl)imidazole, N-(3-nitrobenzyloxycarbonyl)imidazole, N-(4-nitrobenzyloxycarbonyl)imidazole, Imidazole derivatives such as N-(5-methyl-2-nitrobenzyloxycarbonyl)imidazole, N-(4-chloro-2-nitrobenzyloxycarbonyl)imidazole, 1,8-diazabicyclo (5 ,4,0)undecene-7, tertiary amines, quaternary ammonium salts, and mixtures thereof.

Examples of the photo radical generator include azo-based, peroxide-based, acylphosphine oxide-based, alkylphenone-based, oxime ester-based and titanocene-based initiators. Among them, alkylphenone-based, acylphosphine oxide-based, oxime ester-based initiators are preferred, and 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexylphenylketone, 2 -Hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthio Phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[( 4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethyl Benzoyl)phenylphosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2- Methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), and the like.

Examples of the thermal radical generator include 2,2'-azobis(2-methylvaleronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), and the like.

These base generators and radicals can be used alone or in combination like an acid generator.

(V) solvent

The negative photosensitive composition according to the present invention contains a solvent. This solvent is not particularly limited as long as it uniformly dissolves or disperses the polysiloxane, the (meth)acrylic polymer, the (meth)acryloyl group-containing compound, and an additive added as needed. Examples of the solvent that can be used in the present invention include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, and diethylene. Diethylene glycol dialkyl ethers such as glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol Propylene glycol alkyl ether acetates such as monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate, aromatic hydrocarbons such as benzene, toluene and xylene, methyl ethyl ketone, acetone, methyl amyl ketone , Methylisobutyl ketone, ketones such as cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, ethyl lactate, ethyl 3-ethoxypropionate, 3-methoxypropionic acid Esters such as methyl, and cyclic esters such as γ-butyrolactone. Among these, it is preferable to use propylene glycol alkyl ether acetates or esters from the viewpoints of availability, ease of handling, and solubility of polymers. These solvents are used individually or in combination of two or more, respectively, and the amount thereof used varies depending on the application method or the demand for the film thickness after application.

The solvent content rate of the negative photosensitive composition can be arbitrarily adjusted according to a method of applying the composition or the like. For example, in the case of applying the composition by spray coating, the proportion of the solvent in the negative photosensitive composition may be 90% by weight or more. Further, in the slit coating used in the application of a large substrate, it is usually 60% by weight or more, and preferably 70% by weight or more. The characteristics of the negative photosensitive composition of the present invention do not change significantly depending on the amount of the solvent.

(VI) a silicon compound containing a thiol group

The negative photosensitive composition according to the present invention contains a silicon compound containing a thiol group, if necessary. The silicon compound forming the main structure here is not particularly limited, such as polysiloxane, silsesquioxane, polysilazane, polysiloxane, silane, and silanol. Further, it is not limited to an inorganic compound, and an organic silicon compound in which hydrogen of the inorganic silicon compound is substituted with a hydrocarbon group or the like, or an organic compound mainly composed of a hydrocarbon substituted with a siloxy group or a silanol group may be used. In addition, with respect to the silicon compound forming these main structures, the thiol group can be bonded directly or via an arbitrary linking group.

Specifically, the compound containing the following partial structures (a) and (b) in a repeating unit is mentioned.

[SiR ¹ O _1.5 ] (a)

[Si(R ² SH)O _1.5 ] (b)

In the above formulas,

R ¹ is a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 10 carbon atoms,

R ² is a single bond or a hydrocarbon chain having 1 to 10 carbon atoms.

In addition, silicone oligomers, such as X-41-1818, X-41-1810, or X-41-1805 (any brand name, manufactured by Shin-Etsu Chemical Industries, Ltd.), or a silane coupling agent, such as KBM -802, or KBM-803 (any brand name, manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used. Among these, it is preferable that a thiol group is bonded to polysiloxane or silsesquioxane from the viewpoint of compatibility with polysiloxane which is the main component of the composition or crosslinking property by reaction.

When the silicon compound containing a thiol group is a polymeric compound, the weight average molecular weight thereof is preferably 500 to 10,000, more preferably 1,000 to 5,000. In addition, the number of thiol groups per molecule of the compound is not particularly limited, but many are preferable to form a crosslinked structure, and in order to prevent unnecessary reactions from proceeding, the number of thiol groups is preferably not more than a certain value. From this point of view, when the silicon compound containing a thiol group is a polymeric compound, the thiol group per equivalent is preferably 0.2 to 3.5, and preferably 0.5 to 3.2. The amount of the silicon compound containing a thiol group is preferably large in order to maintain good chemical resistance after curing, and is preferably not more than a certain amount in order to maintain storage stability. From this point of view, it is preferable that the blending amount of the polysiloxane and the (meth)acrylic polymer is 0.5 to 50 parts by weight based on 100 parts by weight of the total weight.

(VII) additive

The negative photosensitive composition according to the present invention may contain other additives as necessary. Examples of such additives include a developer dissolution accelerator, a scum remover, an adhesion enhancer, a polymerization inhibitor, an antifoaming agent, a surfactant, or a sensitizer.

The developer dissolution accelerator or scum remover has an action of adjusting the solubility of the formed film in the developer and preventing scum from remaining on the substrate after development. As such additives, crown ethers can be used. As the crown ether, the one having the simplest structure is one represented by the formula (-CH ₂ -CH ₂ -O-) _n . In the present invention, among these, n is preferably 4 to 7. Crown ethers are sometimes called x-crown-y-ethers in which the total number of atoms constituting the ring is x and the number of oxygen atoms contained therein is y. In the present invention, it is preferred to be selected from the group consisting of crown ethers of x = 12, 15, 18, or 21 and y = x/3, and benzo condensates and cyclohexyl condensates thereof. Specific examples of more preferable crown ethers are 21-crown-7-ether, 18-crown-6-ether, 15-crown-5-ether, 12-crown-4-ether, dibenzo-21-crown-7- Ether, dibenzo-18-crown-6-ether, dibenzo-15-crown-5-ether, dibenzo-12-crown-4-ether, dicyclohexyl-21-crown-7-ether, dicyclohexyl -18-crown-6-ether, dicyclohexyl-15-crown-5-ether, and dicyclohexyl-12-crown-4-ether. In the present invention, among these, the one selected from 18-crown-6-ether and 15-crown-5-ether is most preferred. The added amount thereof is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total weight of the polysiloxane and the (meth)acrylic polymer.

When a cured film is formed using the negative photosensitive composition according to the present invention, the adhesion enhancing agent has an effect of preventing the pattern from peeling off due to pressure applied after firing. As the adhesion enhancing agent, imidazoles, silane coupling agents, etc. are preferable, and in the imidazoles, 2-hydroxybenzoimidazole, 2-hydroxyethylbenzoimidazole, benzoimidazole, 2-hydroxyimidazole, imidazole , 2-mercaptoimidazole and 2-aminoimidazole are preferred, and 2-hydroxybenzoimidazole, benzoimidazole, 2-hydroxyimidazole, and imidazole are particularly preferably used.

Known silane coupling agents are suitably used, epoxysilane coupling agents, aminosilane coupling agents, mercaptosilane coupling agents, and the like are exemplified, and specifically, 3-glycidoxypropyltrimethoxysilane, 3-glyci Doxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane Silane, 3-aminopropyltriethoxysilane, 3-ureidepropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, etc. desirable. These may be used alone or in combination of a plurality of them, and the addition amount thereof is preferably 0.05 to 15 parts by weight based on 100 parts by weight of the total weight of the polysiloxane and (meth)acrylic polymer.

Further, as the silane coupling agent, a silane compound having an acid group, a siloxane compound, or the like can also be used. Examples of the acid group include a carboxyl group, an acid anhydride group, and a phenolic hydroxyl group. When containing a monobasic acid group such as a carboxyl group or a phenolic hydroxyl group, it is preferable that a single silicon-containing compound has a plurality of acid groups.

As a specific example of such a silane coupling agent, the following formula B:

Formula B

X _n Si(OR ³ ) _4-n

A compound represented by or a polymer obtained as a polymerization unit thereof can be mentioned. In this case, a plurality of polymerization units from which X or R ³ are different can be used in combination.

In the general formula (B), examples of R ³ include a hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an alkyl group such as n-butyl group. In the formula (A), a plurality of R ³ is contained, but each R ³ may be the same or different.

Examples of X include those having acid groups such as phosphonium, borate, carboxyl, phenol, peroxide, nitro, cyano, sulfo, and alcohol groups, and these acid groups acetyl, aryl, amyl, benzyl, methoxymethyl, mesyl, Tolyl, trimethoxysilyl, triethoxysilyl, triisopropylsilyl, or those protected by a trityl group, and acid anhydride groups may be mentioned.

Among these, those having a methyl group as R ³ and a carboxylic anhydride group as X, such as an acid anhydride group-containing silicone are preferable. More specifically, the compound represented by the following general formula B-1 (X-12-967C (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)), and a structure corresponding to this, is used as the terminal or side chain of a silicon-containing polymer such as silicone. The polymer contained in is preferable. Further, a compound having an acid group such as thiol, phosphonium, borate, carboxyl, phenol, peroxide, nitro, cyano, and sulfo group imparted to the terminal portion of the dimethyl silicone is also preferable. Examples of such compounds include compounds represented by the following formulas B-2 and B-3 (X-22-2290AS and X-22-1821 (any of which are brand names, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)).

Formula B-1

Formula B-2

Formula B-3

When the silane coupling agent contains a silicone structure, if the molecular weight is too large, compatibility with the polysiloxane contained in the composition is insufficient, so that the solubility in the developer is not improved, and the reactive group remains in the film, which can withstand the post process. There is a possibility that there is an adverse effect, such as the inability to maintain. For this reason, the weight average molecular weight of the silicon-containing compound is preferably 5,000 or less, and more preferably 4,000 or less. Further, the polymer corresponding to (B-1) is preferably a relatively small one having a weight average molecular weight of 1,000 or less, but in the case of a polymer containing a silicone structure in other repeating units, it is preferable that the weight average molecular weight is 1,000 or more. In addition, when a silane compound having an acid group, a siloxane compound, or the like is used as a silane coupling agent, the amount thereof is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the total weight of the polysiloxane and (meth)acrylic polymer.

As the polymerization inhibitor, in addition to nitrone, nitroxide radical, hydroquinone, catechol, phenothiazine, phenoxadine, hindered amine and derivatives thereof, ultraviolet absorbers can be added. Among them, as catechol, 4-t-butylcatechol, 3-methoxycatechol, phenothiazine, chlorpromazine, phenoxazine, and hindered amine, TINUVIN 144, 292, 5100 (manufactured by BASF), ultraviolet absorber As examples, TINUVIN 326, 328, 384-2, 400 and 477 (manufactured by BASF) are preferable. These may be used alone or in combination of a plurality of them, and the addition amount thereof is preferably 0.01 to 20 parts by weight based on 100 parts by weight of the total weight of the polysiloxane and (meth)acrylic polymer.

As the antifoaming agent, alcohol (C _1-18 ), higher fatty acids such as oleic acid and stearic acid, higher fatty acid esters such as glycerin monolaurylate, polyethylene glycol (PEG) (Mn 200 to 10,000), polypropylene glycol (PPG) ( Polyethers such as Mn 200 to 10,000), silicone compounds such as dimethyl silicone oil, alkyl-modified silicone oil, and fluoro silicone oil, and organosiloxane surfactants shown in detail below. These may be used alone or in combination of a plurality, and the addition amount thereof is preferably 0.1 to 3 parts by weight based on 100 parts by weight of the total weight of the polysiloxane and (meth)acrylic polymer.

Further, the negative photosensitive composition of the present invention may contain a surfactant as necessary. Surfactants are added for the purpose of improving coating properties and developability. Examples of the surfactant that can be used in the present invention include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene cetyl ether, and polyoxyethylene alkyl ethers. Acetylene glycol derivatives such as oxyethylene fatty acid diester, polyoxy fatty acid monoester, polyoxyethylene polyoxypropylene block polymer, acetylene alcohol, acetylene glycol, polyethoxylate of acetylene alcohol, and polyethoxylate of acetylene glycol, containing fluorine Surfactants, such as Florade (brand name, manufactured by Sumitomo 3M Co., Ltd.), Megapac (brand name, manufactured by DIC Corporation), sulfron (brand name, manufactured by Asahi Glass Co., Ltd.), or organic siloxane interface An activator, for example, KP341 (brand name, manufactured by Shin-Etsu Chemical Co., Ltd.), etc. are mentioned. Examples of the acetylene glycol include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octin-3,6-diol, 2,4,7 ,9-tetramethyl-5-decin-4,7-diol, 3,5-dimethyl-1-hexin-3-ol, 2,5-dimethyl-3-hexine-2,5-diol, 2,5- Dimethyl-2,5-hexanediol, etc. are mentioned.

In addition, as anionic surfactants, ammonium salts or organic amine salts of alkyldiphenyletherdisulfonic acid, ammonium salts or organic amine salts of alkyldiphenylethersulfonic acid, ammonium salts or organic amine salts of alkylbenzenesulfonic acid, polyoxyethylene alkyl ether sulfuric acid And an ammonium salt or an organic amine salt, an ammonium salt or an organic amine salt of an alkyl sulfuric acid.

Further, examples of the amphoteric surfactant include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauryl acid amide propylhydroxysulfone betaine, and the like.

These surfactants may be used alone or in combination of two or more, and the blending amount thereof is usually 50 to 10,000 ppm, preferably 100 to 1,000 ppm with respect to the negative photosensitive composition of the present invention.

Moreover, a sensitizer can be added to the negative photosensitive composition of this invention as needed. As sensitizers preferably used in the negative photosensitive composition of the present invention, coumarin, ketocoumarin and derivatives thereof, thiopyryllium salts, acetphenones, etc., specifically, p-bis(o-methylstyryl) Benzene, 7-dimethylamino-4-methylquinolone-2,7-amino-4-methylcoumarin, 4,6-dimethyl-7-ethylaminocoumarin, 2-(p-dimethylaminostyryl)-pyridylmethylio Didide, 7-diethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 2,3,5,6-1H,4H-tetrahydro-8-methylquinolidino-<9,9a,1-gh >coumarin, 7-diethylamino-4-trifluoromethylcoumarin, 7-dimethylamino-4-trifluoromethylcoumarin, 7-amino-4-trifluoromethylcoumarin, 2,3,5,6- 1H,4H-tetrahydroquinolidino-<9,9a,1-gh>coumarin, 7-ethylamino-6-methyl-4-trifluoromethylcoumarin, 7-ethylamino-4-trifluoromethylcoumarin , 2,3,5,6-1H,4H-tetrahydro-9-carboethoxyquinolidino-<9,9a,1-gh>coumarin, 3-(2'-N-methylbenzimidazolyl) -7-N,N-diethylaminocoumarin, N-methyl-4-trifluoromethylpiperidino-<3,2-g>coumarin, 2-(p-dimethylaminostyryl)-benzothiazolylethyl Iodide, 3-(2'-benzimidazolyl)-7-N,N-diethylaminocoumarin, 3-(2'-benzothiazolyl)-7-N,N-diethylaminocoumarin, and the following And sensitizing dyes such as pyryllium salt and thiopyryllium salt represented by the formula. By adding a sensitizing dye, patterning using an inexpensive light source such as a high-pressure mercury lamp (360 to 430 nm) becomes possible. The added amount thereof is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total weight of the polysiloxane and (meth)acrylic polymer.

Further, as a sensitizer, an anthracene skeleton-containing compound can also be used. Specifically, a compound represented by the following general formula (C) can be mentioned.

Formula C

In Formula C,

R ³¹ are each independently a substituent selected from the group consisting of an alkyl group, an aralkyl group, an allyl group, a hydroxyalkyl group, an alkoxyalkyl group, a glycidyl group, and a hydrogenated alkyl group,

Each R ³² is independently a substituent selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfonic acid group, a hydroxyl group, an amino group, and a carboalkoxy group,

each k is an integer independently selected from 0 and 1 to 4.

A sensitizer having such an anthracene skeleton is also disclosed in Patent Documents 2 or 3 and the like. When using such a sensitizer having an anthracene skeleton, the amount thereof is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the total weight of the polysiloxane and (meth)acrylic polymer.

Further, to the negative photosensitive composition according to the present invention, a stabilizer can be added as needed. As a stabilizer, it can be arbitrarily selected and used from those generally used, but in the composition according to the present invention, an aromatic amine is preferred because of its high stabilizing effect. Among these aromatic amines, pyridine derivatives are preferred, and particularly those having relatively bulky substituents at the 2nd and 6th positions are preferred. Specifically, the following are mentioned.

Cured film formation method

The method for forming a cured film according to the present invention includes applying the negative photosensitive composition to a substrate surface and heat-curing the negative photosensitive composition. The method of forming the cured film will be described in the order of steps as follows.

(1) Application process

First, the above negative photosensitive composition is applied to a substrate. The formation of the coating film of the photosensitive composition in the present invention can be carried out by any method known conventionally as a method of applying the photosensitive composition. Specifically, it can be arbitrarily selected from immersion coating, roll coating, bar coating, brush coating, spray coating, doctor coating, flow coating, spin coating, and slit coating. Further, as the substrate to which the composition is applied, a suitable substrate such as a silicone substrate, a glass substrate, and a resin film can be used. Various semiconductor elements or the like may be formed on these substrates as necessary. When the substrate is a film, gravure application can also be used. If desired, a drying process may be separately provided after the coating film. Further, if necessary, the coating process can be repeated once or two or more times, and the film thickness of the formed coating film can be set as desired.

(2) Pre-baking process

After forming a coating film by applying a negative photosensitive composition, it is preferable to dry the coating film and prebak (pre-heat treatment) the coating film in order to reduce the residual amount of the solvent in the coating film. The pre-baking process is generally at a temperature of 50 to 150°C, preferably 90 to 120°C, for 10 to 300 seconds, preferably 30 to 120 seconds for a hot plate, and 1 to for a clean oven. This can be done for 30 minutes.

(3) Exposure process

After forming the coating film, light irradiation is performed on the surface of the coating film. As the light source used for light irradiation, any one conventionally used in the pattern formation method can be used. Examples of such a light source include lamps such as high-pressure mercury lamps, low-pressure mercury lamps, metal halide and xenon, laser diodes, and LEDs. As the irradiation light, ultraviolet rays such as g-rays, h-rays and i-rays are usually used. Except for ultra-fine processing such as semiconductors, it is common to use 360 to 430 nm of light (high pressure mercury lamp) for patterning of several µm to tens of µm. Among these, in the case of a liquid crystal display device, light of 430 nm is often used. In this case, as described above, it is advantageous to combine the sensitizing dye with the negative photosensitive composition of the present invention. The energy of the irradiation light is also different depending on the light source and the film thickness of the coating film, but is generally 5 to 2000 mJ/cm 2, preferably 10 to 1000 mJ/cm 2. When the irradiation light energy is lower than 10 mJ/cm 2, sufficient resolution may not be obtained. Conversely, when it is higher than 2000 mJ/cm 2, exposure may become excessive and halation may occur.

In order to irradiate light in a pattern, a general photomask can be used. Such a photomask can be arbitrarily selected from known ones. The environment at the time of irradiation is not particularly limited, but generally, an ambient atmosphere (in air) or a nitrogen atmosphere may be used. Further, in the case of forming a film on the entire surface of the substrate, light irradiation may be performed on the entire surface of the substrate. In the present invention, the patterned film also includes a case where a film is formed on the entire surface of the substrate.

(4) heating process after exposure

After exposure, in order to accelerate the reaction between the polymers in the film by the reaction initiator generated at the exposed location, post-exposure baking may be performed as necessary. Unlike the heating process (6) described later, this heat treatment is not performed to completely cure the coating film, but is performed so that only the desired pattern remains on the substrate after development, and other parts can be removed by development. . Therefore, it is not essential in the present invention.

In the case of heating after exposure, a hot plate, an oven, or a furnace may be used. The heating temperature should not be excessively high because it is not preferable that the acid in the exposed region generated by light irradiation diffuses to the unexposed region. From this point of view, the range of the heating temperature after exposure is preferably 40 to 150°C, and more preferably 60 to 120°C. If necessary, stepwise heating may be applied to control the curing rate of the composition. In addition, the atmosphere at the time of heating is not particularly limited, but for the purpose of controlling the curing rate of the composition, it can be selected from inert gases such as nitrogen, under vacuum, under reduced pressure, and oxygen gas. In addition, the heating time is preferably more than a certain level in order to keep the uniformity of the temperature history in the wafer surface higher, and in order to suppress the diffusion of the generated acid, it is preferably not too long. From this point of view, the heating time is preferably 20 to 500 seconds, more preferably 40 to 300 seconds.

(5) development process

After exposure, heating is performed after exposure as necessary, and then the coating film is developed. As a developer used during development, any developer conventionally used for developing a photosensitive composition can be used. In the present invention, an aqueous TMAH solution is used to specify the dissolution rate of the polysiloxane, but the developer used when forming the cured film is not limited thereto. As a preferable developer, alkali, which is an aqueous solution of alkaline compounds such as tetraalkylammonium hydroxide, choline, alkali metal hydroxide, alkali metal metasilicate (hydrate), alkali metal phosphate (hydrate), ammonia, alkylamine, alkanolamine, and heterocyclic amine A developer may be mentioned, and a particularly preferable alkaline developer is an aqueous solution of tetramethylammonium hydroxide, an aqueous potassium hydroxide solution, or an aqueous sodium hydroxide solution. These alkaline developing solutions may further contain a water-soluble organic solvent such as methanol or ethanol, or a surfactant as necessary.

The developing method can also be arbitrarily selected from conventionally known methods. Specifically, methods such as immersion (dip) in a developer, paddle, shower, slit, cap coating, spray, and the like can be mentioned. It is preferable to wash with water after the development is carried out with a developer solution from which a pattern can be obtained by this phenomenon.

(6) heating process

After development, it is cured by heating the obtained patterned film. As the heating device used in the heating step, the same one used for heating after the above exposure can be used. The heating temperature in this heating step is not particularly limited as long as it is a temperature at which the coating film can be cured, and can be arbitrarily determined. However, if the silanol group remains, the chemical resistance of the cured film may become insufficient, or the dielectric constant of the cured film may increase. In this respect, a relatively high heating temperature is generally selected. However, the negative photosensitive composition according to the present invention can be cured at a relatively low temperature. Specifically, it is preferable to cure by heating at 360°C or less, and in order to maintain a high film residual rate after curing, the curing temperature is more preferably 300°C or less, and particularly preferably 150°C or less. On the other hand, in order to accelerate the curing reaction to obtain a sufficient cured film, the curing temperature is preferably 70° C. or higher, more preferably 100° C. or higher, and particularly preferably 110° C. or higher. In addition, the heating time is not particularly limited, and is generally 10 minutes to 24 hours, preferably 30 minutes to 3 hours. In addition, this heating time is a time after the temperature of the pattern film reaches a desired heating temperature. Usually, it takes about several minutes to several hours until the pattern film reaches the desired temperature at the temperature before heating.

The cured film thus obtained can achieve excellent transparency, chemical resistance, environmental resistance, and the like. For example, a film cured at 120°C has a film loss of 5% or less at 280°C, and has sufficient heat resistance, and the cured film has a light transmittance of 95% or more and a relative dielectric constant of 4 or less. For this reason, it has light transmittance and relative dielectric constant characteristics that are not found in conventional acrylic materials, and is a flat panel display (FPD), etc., a planarization film for various devices as described above, an interlayer insulating film for low temperature polysilicon, or a buffer coating film for IC chips, It can be suitably used in a variety of ways as a transparent protective film or the like.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited at all by these Examples and Comparative Examples.

<Example 1>

After prebaking, the dissolution rate in 2.38% TMAH aqueous solution is 1,200 Å/sec, the weight average molecular weight of 1,750 polysiloxane S1, the dissolution rate in 5.00% TMAH aqueous solution is 500 Å/sec, the weight average molecular weight 2,700 polysiloxane S2, acrylic having a vinyl group Polymer A1-1 (weight average molecular weight 12,000, double bond equivalent 24 g/eq, acid value 19 mgKOH/g), acrylic polymer A2-1 having a carboxyl group (weight average molecular weight 7,500, acid value 120 to 130 mgKOH/g) was 10:20:40 Mixing at a ratio of :30 to obtain a polymer mixture. To this polymer mixture, 25 parts by weight and 12 parts by weight of tris(2-acryloxyethyl)isocyanurate (M1) and dipentaerythritol hexaacrylate (M2) as a (meth)acryloyl group-containing compound, respectively , 6.0 parts by weight of Irgacure OXE-02 (PI) as a polymerization initiator, and 8 parts by weight of a silicon compound SQ containing a thiol group were added. Here, the compound SQ is a silsesquioxane positive condensate having a thiol group, a thiol group is bonded to a silicon atom through a butylene group, and the thiol group equivalent is 535 g/eq. Further, 0.3 parts by weight of KF-53 manufactured by Shin-Etsu Chemical Co., Ltd. was added as a surfactant, and it was adjusted to a 35% PGMEA solution to obtain a negative photosensitive composition. On the other hand, the blending ratio (parts by weight) of each component here is based on 100 parts by weight of the total weight of the polysiloxane and the (meth)acrylic polymer.

The negative photosensitive composition was applied onto a silicon wafer by spin coating and prebaked on a hot plate for 90 seconds at 70[deg.] C. after application, and adjusted to a film thickness of 1.5 [mu]m. After confirming that the obtained film after prebaking had no tuck or tack, it was exposed at 20 mJ/cm 2 using an i-line exposure machine, immersed in a 2.38% TMAH aqueous solution for 60 seconds, and rinsed with pure water for 30 seconds. . As a result, it was confirmed that the 10 μm line and space (L/S) pattern and the contact hole (C/H) pattern were missing. After pattern formation, plastic curing was performed at 120° C., and as a result of confirming with an optical microscope, a 10 µm pattern was maintained. In addition, after the obtained pattern was heated to 60° C., it was immersed in a 3% KOH solution for 3 minutes, and the presence or absence of the pattern was confirmed, confirming that the pattern was maintained. In addition, as a result of storing the composition at a room temperature of 23° C. and a humidity of 45%, changes in sensitivity and pattern shape did not appear after one week.

<Examples 2 to 13, Comparative Examples 1 to 4>

For Example 1, as shown in Table 1, a negative photosensitive composition in which the composition was changed was prepared, and evaluated in the same manner as in Example 1. The obtained results were as shown in Table 1.

In the table:

Acrylic polymer A1-2: Acrylic polymer having a vinyl group (weight average molecular weight 10,000, double bond equivalent 105 g/eq, acid value 20 mgKOH/g)

Acrylic polymer A2-2: acrylic polymer having a carboxyl group (weight average molecular weight 15,000, acid value 120 to 130 mgKOH/g)

The evaluation criteria of each characteristic were as follows.

After development Residue

The film surface after development was observed and evaluated with an optical microscope.

A: No residue

B: There is some residue at the end of the pattern

C: There is a thin layered residue

D: There is a thick layered residue

After development or after curing Film remaining rate

The film thickness before development and the film thickness after development or after curing were observed with an optical microscope, and the rate of change thereof was evaluated.

A: more than 90%

B: 70% or more

C: 50% or more

D: less than 50%

N/A: Not measurable (no residual film)

Stickiness of the membrane

The probe was brought into contact with the membrane surface and observed with the naked eye.

A: There is no stickiness, and no cloudiness is observed even when it touches the film surface

B: When contacting the membrane surface, a slight haze is observed, but a level that is practical

C: It has a lot of stickiness and is not practical

Chemical resistance

After the pattern was heated to 60°C, it was immersed in 3% KOH solution for 3 minutes, the presence or absence of the pattern was observed with an optical microscope, and the residual ratio of the film before and after immersion was evaluated.

A: more than 90%

B: 70% or more

C: 50% or more

D: less than 50%

N/A: Not measurable (no residual film)

Claims (14)

(Ia) The film after prebaking is soluble in a 5% by weight aqueous solution of tetramethylammonium hydroxide, and the dissolution rate thereof is 3,000 Å/sec or less.
(Ib) a second polysiloxane having a dissolution rate of 150 Å/sec or more in a 2.38 wt% tetramethylammonium hydroxide aqueous solution of the film after prebaking
A polysiloxane mixture containing no reactive groups other than silanol groups or alkoxysilyl groups;
(Meth)acrylic polymers containing a repeating unit having an unsaturated bond, a repeating unit having an acid group, or both and having a weight average molecular weight of 2,000 to 100,000;
A compound containing two or more (meth)acryloyl groups having a molecular weight of 1500 or less;
Polymerization initiator; And
It contains a solvent,
A negative photosensitive composition, characterized in that the blending ratio of the polysiloxane mixture and the (meth)acrylic polymer is 90:10 to 10:90 based on mass. The negative photosensitive composition according to claim 1, wherein the weight average molecular weight of the polysiloxane mixture contained in the composition is 5,000 or less. The method according to claim 1 or 2, comprising 3 to 50 parts by weight of a compound containing two or more (meth)acryloyl groups based on 100 parts by weight of the total weight of the polysiloxane mixture and the (meth)acrylic polymer. , Negative photosensitive composition. The (meth)acrylic polymer according to claim 1 or 2, wherein the (meth)acrylic polymer is a (meth)acrylic polymer comprising a repeating unit having the unsaturated bond and a (meth)acrylic polymer comprising a repeating unit having the acid group. Consisting of, the negative photosensitive composition. The negative photosensitive composition according to claim 1 or 2, further comprising a silicon compound containing a thiol group. The negative photosensitive composition according to claim 5, wherein the silicon compound containing a thiol group is a polymer containing a thiol group-containing siloxane as a repeating unit. The negative photosensitive composition according to claim 5, wherein 0.5 to 50 parts by weight of a silicon compound containing the thiol group is contained based on 100 parts by weight of the total weight of the polysiloxane mixture and the (meth)acrylic polymer. The negative photosensitive composition according to claim 1 or 2, wherein the polysiloxane mixture and the (meth)acrylic polymer contain 0.001 to 10 parts by weight of a polymerization initiator based on 100 parts by weight of the total weight of the (meth)acrylic polymer. The negative photosensitive composition according to claim 1 or 2, further comprising an additive selected from the group consisting of a developer dissolution accelerator, a scum remover, an adhesion enhancer, a polymerization inhibitor, an antifoaming agent, a surfactant, and a photosensitizer. A method for producing a cured film comprising applying the negative photosensitive composition according to claim 1 or 2 to a substrate to form a coating film, and exposing the coating film to develop. The method for producing a cured film according to claim 10, wherein after development, heating is performed at a temperature of 70°C or more and 360°C or less in order to cure the coating film. A cured film formed from the negative photosensitive composition according to claim 1 or 2. An element comprising the cured film according to claim 12. delete