KR20060103132A - Photosensitive resin composition - Google Patents

Abstract

Provided is a photosensitive resin composition which is excellent in compatibility with the solvent for the photosensitive resin composition, has high surface tension lowering ability, high surface smoothing ability, and contains a leveling agent for photosensitive resin composition having high stability.

0.01 to 20% by weight of (poly) glycerine-modified silicone formed by combining ABA with structural unit A, which is an organopolysiloxane residue represented by Formula 1 below, and structural unit B, which is a (poly) glycerine derivative residue represented by Formula 2 below: It contains.

<Formula 1>

<Formula 2>

[In the meal,

R ¹ is, independently from each other, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group having 1 to 10 carbon atoms which may be substituted with halogen,

x is an integer from 0 to 100,

α is 1 or 2,

R ² is independently an alkylene group having 2 to 11 carbon atoms,

s is an integer from 1 to 11.]

Photosensitive resin composition, leveling agent, (poly) glycerin modified silicone, flatness

Description

Photosensitive Resin Composition

1 is an IR chart of an ABA polyglycerol modified silicone No. 3;

<Patent Document 1> Japanese Unexamined Patent Application Publication No. 2004-87900

<Patent Document 2> Japanese Patent Application Laid-Open No. 2004-4531

The present invention relates to a photosensitive resin composition containing a (poly) glycerine-modified silicone useful as a leveling agent for a photosensitive resin composition, and more particularly, to a photosensitive resin composition applicable to various resists such as photoresist, etching resist and pigment dispersion resist. It relates to a photosensitive resin composition containing a leveling agent for use, and widely used in various fields such as the electronics industry and the printing industry.

Background Art Conventionally, photosensitive resin compositions containing resin components, photoinitiators, sensitizers, crosslinking agents and the like have been widely used in various fields such as the electronics industry, the printing industry, the paint and ink industry, and the metal processing industry. The main use of the specific use is the photoresist for partial etching of metal, photoresist for precision electronic circuit manufacture, such as LSI, the resin plate manufacturing material for printing, the screen printing ink, the coloring photoresist for color filter manufacture, etc. In recent years, with the miniaturization and the high density of precision electronic circuits, product development for the purpose of the more sensitive and high resolution with respect to the photosensitive resin composition is advanced.

 There exist two types of said photosensitive resin composition: the positive type which an exposure part is removed at the time of image development process, and a positive pattern is obtained, and the negative type which an unexposed part is removed at the time of image development process, and a negative pattern is obtained. Generally, the negative type has better sensitivity, adhesion to the substrate, and chemical resistance than the positive type, and the positive type has better resolution and dry etching resistance than the negative type.

The preparation of the resist pattern usually includes the steps of surface treatment of the substrate, coating of the resist, prebaking, exposure, development, postbaking, etching of the underlying substrate, and peeling of the resist (washing). In accordance with this, the resolution, residual film characteristic, dimensional controllability, adhesiveness, and the like of the resist greatly change.

As a coating method of a resist, there exist methods, such as spin coating, spray coating, roll coater coating, and dip coating, but spin coating is the most preferable at present in the uniformity and stability of a coating film thickness.

The coating film thickness of a resist varies greatly according to the kind of solvent in a resist solution, solvent content, the kind and content of resist solid content, the viscosity of the said solid content, etc. In addition, variations in the coating film thickness of the resist directly affect the dimensions of the product. In addition, the uniformity of the coating film surface of the resist is influenced by the surface tension, viscosity, solvent volatility, and the like of the resist solution.

In recent years, in order to control the coating film thickness of a resist more highly and to improve the uniformity of coating film thickness, the use of a high boiling point solvent and the addition of a leveling agent (smoothing agent) are examined simultaneously with the reevaluation of the environment of a resist coating process. It is becoming. When apply | coating a resist, as a leveling agent, nonionic surfactant or silicone type surfactant, such as polyether modified silicone and fluoropolyether comodified silicone, is mainly used.

Related technical documents, such as Patent Document 1, describe resist pattern smoothing materials containing nonionic surfactants such as alkoxylates, fatty acid esters, and amides.

In addition, Patent Document 2 describes a photosensitive resin composition containing a surfactant selected from a silicon-based surfactant, a fluorine-based surfactant, and a silicon-based surfactant having a fluorine atom.

However, existing nonionic surfactants and polyether-modified silicones exhibit insufficient compatibility with the solvent for the photosensitive resin composition and exhibit sufficient surface tension lowering ability and surface smoothness when used in the photosensitive resin composition as a leveling agent. Could not.

Therefore, fluorine polyether co-modified silicone is used as a leveling agent for the photosensitive resin composition instead of these, but since this has a problem in the safety of the fluorine-substituted alkyl group, a replacement product was required.

Therefore, this invention is the photosensitive resin composition which is excellent in compatibility with the solvent for photosensitive resin compositions, and has a high level of surface tension fall ability, surface smoothness, and high stability, The photosensitive resin composition containing a high stability, ie, a base material It is an object of the present invention to provide a photosensitive resin composition which is excellent in malleability that is easy to spread on a phase, can be applied uniformly without generating coating unevenness, and has high stability.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, it discovered that the said subject can be solved by introducing a (poly) glycerol structure into a silicone main chain and using this as a leveling agent for photosensitive resin compositions. Based on this, various examination was repeated and this invention was completed.

That is, in this invention, the structural unit A which is the organopolysiloxane residue represented by following General formula (1), and the structural unit B which is the (poly) glycerine derivative residue represented by following General formula (2) are couple | bonded with ABA (poly) glycerin modified silicone It relates to a photosensitive resin composition containing 0.01 to 20% by weight.

[In the meal,

R ¹ is, independently from each other, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group having 1 to 10 carbon atoms which may be substituted with halogen,

x is an integer from 0 to 100,

α is 1 or 2,

R ² is independently an alkylene group having 2 to 11 carbon atoms,

s is an integer from 1 to 11.]

Best Mode for Carrying Out the Invention

The photosensitive resin composition of the present invention is a (poly) glycerin-modified silicone (hereinafter referred to as ABA-type (poly) glycerine-modified silicone) in which the structural unit A and the structural unit B are bonded by ABA as a leveling agent for the photosensitive resin composition. It is characterized by containing. The structural unit A of the ABA type (poly) glycerin modified silicone is an organopolysiloxane residue represented by the formula (1).

In Formula 1, R ¹ is independently of each other, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group having 1 to 10 carbon atoms which may be substituted with halogen. Examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Aryl groups, such as a phenyl group and a tolyl group; Aralkyl groups such as benzyl and phenethyl; Groups in which a part of hydrogen of the hydrocarbon group is substituted with halogen, such as a trifluoropropyl group and a nonafluorooctyl group, are preferable, and a methyl group, an ethyl group, a propyl group and a butyl group are preferable.

In Formula 1, x is an integer of 0 to 100, preferably an integer of 0 to 20, more preferably an integer of 0 to 10. α is 1 or 2.

The organopolysiloxane residue of this structural unit A is alpha-organo which has a hydrosilyl group (Si-H group) in one terminal, for example as mentioned later about the manufacturing method of ABA type (poly) glycerol modified silicone. It may be derived from hydrogenpolysiloxanes.

The structural unit B of the ABA type (poly) glycerine modified silicone is a (poly) glycerine derivative residue represented by the formula (2).

In Formula 2, R ² independently of each other, an alkylene group having 2 to 11 carbon atoms, for example, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene Straight chain alkylene groups such as groups; Branched-chain alkylene groups, such as a propylene group, an ethylethylene group, 2-methyl trimethylene group, and 2-methyl tetramethylene group, are mentioned, For the reason of the effect as a leveling agent for photosensitive resin compositions, ease of manufacture, etc., Preferably, It is a C2-C5 linear alkylene group, More preferably, it is a C3, ie, trimethylene group.

In addition, s is an integer of 1-11, Preferably it is an integer of 1-8, More preferably, it is an integer of 2-4.

The skeletal structure of the residue of the (poly) glycerol derivative of the formula (2) may be a straight chain polymerized from the entire glycerine in the terminal OH group, or may be a branched polymerized from the OH group bonded to the secondary carbon of the glycerin. have.

However, in consideration of the effect as a leveling agent for the photosensitive resin composition, ease of manufacture, and the like, the structural unit B is particularly preferably a linear (poly) polyglycerin derivative residue represented by the following general formula (3). In addition, in general formula (3), R <^2> is trimethylene group and s is an integer of 1-8.

The combination of x in the formula (1) and s in the formulas (2) and (3) is not particularly limited, and may be any combination. However, when α is 1, x is an integer of 0 to 10 as the leveling agent for the photosensitive resin composition. and s is a combination of 3 or 4, and when alpha is 2, it is especially preferable that it is a combination of x is an integer of 0-5, and s is 3 or 4.

The (poly) glycerin derivative residue of structural unit B can be derived from (poly) glycerine derivatives having two alkenyl groups (2 to 11 carbon atoms), especially allyl groups, in one molecule, as described below.

ABA type (poly) glycerin modified silicone is the (alpha) -organohydrogenpolysiloxane which has a hydrosilyl group at one terminal, and the (poly) glycerol derivative which has two alkenyl groups (C2-C11) in 1 molecule, said alpha It can synthesize | combine by addition-reacting so that the molar ratio (SiH group / alkenyl group) of the hydrosilyl group of organohydrogenpolysiloxane and the alkenyl group of the said (poly) glycerin derivative may be 0.5 or more and less than 1.5, Preferably it is 0.8 or more and less than 1.2.

As (alpha)-organohydrogenpolysiloxane which has a hydrosilyl group in one terminal, the compound represented by AH which H couple | bonded with the structural unit A which is the organopolysiloxane residue mentioned above is mentioned. For example, MM ^H , MD ₁ M ^H , MD ₃ M ^H , M ^C4H9 D ₉ M ^H , M ^C4H9 D ₁₈ M ^H can be used in order, represented by the following Chemical Formulas 4 to 8. However, in the present specification, (H ₃ C) refers to a ₃ SiO _1/2 group as M, a (H ₃ C) ₂ SiO group as D, and a unit in which one of the methyl groups in M and D is hydrogen, respectively, M ^H and D ^H. Mark it. In addition, the unit which substituted one of the methyl groups in M and D with the substituent R is described with M ^R and D ^R , respectively.

In addition, as a (poly) glycerol derivative which has two alkenyl groups in 1 molecule, in the said structural unit B, instead of the alkylene group of R <^2> , a vinyl group, an allyl group, isopropenyl group, 2-methylallyl group, 3- Those having an alkenyl group having 2 to 11 carbon atoms such as a butenyl group, that is, those represented by the following formula (9) can be used. In addition, in general formula (9), R <^3> is a C2-C11 alkenyl group mutually independently, and s is an integer of 1-11.

It is preferable that the double bond of this alkenyl group exists in the terminal from the point which raises the reactivity with the structural unit A, and suppresses generation | generation of a by-product, and especially an allyl group is preferable.

Specifically, as a (poly) glycerin derivative having two alkenyl groups in one molecule, a (poly) glycerin derivative represented by the following formula (10) (s is an integer of 1 to 11), and the following formula 11 and the formula (12) Those having a diglycerin skeleton and a triglycerine skeleton represented can be preferably used.

The (poly) glycerol derivative having two alkenyl groups in one molecule is, for example, polyglycerol such as glycerin or diglycerine, triglycerine, allyl glycidyl ether, etc. in the presence of an alkali catalyst such as potassium hydroxide or sodium hydroxide. After the reaction, the neutralization of the alkali catalyst after the reaction, it can be obtained by distilling off the low boiling point fraction. In that case, it is preferable to control the reaction temperature at 60-120 degreeC.

In order to make the hydrosilyl group of (alpha)-organohydrogenpolysiloxane and two alkenyl groups of (poly) glycerine derivative easily react, addition reaction of (alpha)-organohydrogen polysiloxane and (poly) glycerine derivative is platinum-based. It is preferable to carry out in the presence of a catalyst or a rhodium-based catalyst. Examples of preferred catalysts include chloroplatinic acid, alcohol-modified platinum chloride, and chloroplatinic acid-vinylsiloxane complexes. Although the usage-amount of a catalyst can be made into the minimum amount effective as a catalyst, it is preferable that it is 50 ppm or less in especially platinum or rhodium amount, and it is especially preferable that it is 20 ppm or less.

The said addition reaction can also be performed in an organic solvent as needed. Examples of the organic solvent include aliphatic alcohols such as methanol, ethanol, 2-propanol and butanol, aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane and cyclohexane, dichloromethane, Halogenated hydrocarbons, such as chloroform and carbon tetrachloride, etc. are mentioned.

In the addition reaction, an antioxidant such as tocopherol or 2,6-di-t-butyl-p-cresol (BHT) may be added. Moreover, in order to suppress the side reaction between hydrosilyl group and OH group, it is preferable to use pH adjusters, such as sodium acetate and potassium acetate. Moreover, after the said addition reaction, you may perform alkylation by the removal of the allyl ether group by weak hydrochloric acid, or a hydrogenation reaction by a well-known method.

Although the reaction conditions of the said addition reaction are not specifically limited, It is preferable to make it react for 1 to 10 hours under reflux. Moreover, it is preferable that reaction temperature is 50-120 degreeC. The reaction rate of the addition reaction can be easily confirmed by the hydrogen gas generation amount and the infrared absorption spectrum in the reaction system. If the addition reaction is carried out as described above and the desired addition reaction rate is reached, the desired ABA type (poly) glycerin-modified silicone is obtained by distilling off the reaction solvent by a conventional method as necessary.

The photosensitive resin composition of this invention is a dye, pigment, surfactant, stabilizer, etc. as needed, in addition to the said ABA type (poly) glycerol modified silicone which is a leveling agent for photosensitive resin compositions, a resin component, a photoinitiator, a sensitizer, a crosslinking agent, etc. as needed. It contains various additives.

The resin component is not particularly limited and may be appropriately selected from conventionally known ones such as novolak resins, polyimide silicone resins, polyacrylates, polymethacrylates, polyolefin sulfones, polyvinylphenols, and polyvinylacetates. Can be.

It does not specifically limit as said photoinitiator and a sensitizer, It is suitable from conventionally well-known things, such as an anthraquinone type compound, a benzophenone, an acetophenone type compound, a benzoin type compound, a thioxanthone type compound, a coumarin type compound, benzoic acid ester, etc. Can be used.

It does not specifically limit as said crosslinking agent, It can select suitably from conventionally well-known things, such as a melamine type compound and a urea type compound, and can use.

In using the photosensitive resin composition of this invention, the said composition is dissolved in an organic solvent and used. As such an organic solvent, if it is a solvent which has sufficient solubility with respect to the said composition, and provides favorable coating film property, it can use without a restriction | limiting in particular. For example, cellosolve solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate Propylene glycol solvents such as propylene glycol dimethyl ether and propylene glycol monoethyl ether acetate, ester solvents such as butyl acetate, amyl acetate, methyl lactate, ethyl lactate, ethyl 3-methoxypropionate and ethyl 3-ethoxypropionate; Alcohol solvents such as hexanol and diacetone alcohol, ketone solvents such as cyclohexanone and methyl amyl ketone, ether solvents such as methylphenyl ether and diethylene glycol dimethyl ether, N, N-dimethylformamide and N-methyl High polar solvents, such as pyrrolidone, or these mixed solvent, etc. are mentioned.

As for the usage-amount of the said organic solvent, the range of 1-20 times, especially 1-15 times by weight ratio with respect to the total amount of solid content (novolak resin etc.) in the photosensitive resin composition of this invention is preferable.

Content of ABA type (poly) glycerol modified silicone is 0.01 to 20 weight% with respect to the photosensitive resin composition of this invention. When content of ABA type (poly) glycerol modified silicone is less than 0.01 weight%, the interface tension lowering effect of ABA type (poly) glycerol modified silicone may become inadequate. On the other hand, when it exceeds 20 weight%, ABA type (poly) glycerine modified silicone may not fully be dissolved.

The said ABA type (poly) glycerol modified silicone can be applied to any photosensitive resin composition of positive type and negative type as a leveling agent for photosensitive resin compositions.

In order to form a resist pattern using the photosensitive resin composition of this invention, it can carry out by employing a well-known lithography technique. For example, first, the photosensitive resin composition of this invention which melt | dissolved in the organic solvent on the board | substrates, such as a silicon wafer or the silicon wafer in which the metal film was formed by sputtering or plating, was apply | coated by methods, such as spin coating, and 80-130. Prebaking is carried out under the conditions of 50 ° C. and 50 to 600 seconds to form a resist film having a thickness of 1 to 50 μm, preferably 5 to 30 μm, and more preferably 10 to 25 μm.

Subsequently, a mask for forming a desired pattern is covered on the resist film, and high energy rays or electron beams having a wavelength of 500 nm or less, such as i-rays and g-rays, are exposed at an exposure dose of about 1 to 5,000 mJ / cm ² , preferably 100 To 2,000 mJ / cm ² . After that, postexposure baking (PEB) may be performed on the resist film on a hot plate at 60 to 150 ° C. for 1 to 10 minutes, preferably at 80 to 120 ° C. for 1 to 5 minutes.

Subsequently, immersion is carried out for 0.5 to 20 minutes, preferably 1 to 10 minutes, using a developing solution of an aqueous alkali solution such as 0.1 to 5% by weight, preferably 2 to 3% by weight of tetramethylammonium hydroxide (TMAH). The target resist pattern is formed on a substrate by developing in a conventional method such as a) method, a paddle method, a spray method, or the like. After the development, postbaking may be performed at 50 to 100 ° C. for about 10 to 600 seconds.

Subsequently, the substrate on which the resist pattern is formed is ashed by oxygen plasma or the like to remove minute resist residues on the resist pattern, and at the same time, the surface of the resist is hydrophilized, followed by electrolytic or electroless plating. By performing this, a metal pattern can be obtained on the substrate. Moreover, as a kind of plating, Au, Cu, Fe, Ni, etc. are mentioned, Its film thickness is 1-40 micrometers, It is preferable to set it as 5-20 micrometers especially.

<Example>

Although an Example is given to the following and this invention is demonstrated to it in detail, this invention is not restrict | limited to these at all.

[Production of Polyglycerol Derivatives Having Two Allyl Groups in One Molecule]

By the method mentioned above, the polyglycerol derivative (henceforth diallylated polyglycerol) which has two allyl groups in 1 molecule was manufactured. That is, 1 ml of monoglycerine and 2 ml of allylglycidyl ether are reacted at 60 to 120 ° C. in the presence of a potassium hydroxide catalyst, followed by neutralization of the catalyst, followed by distillation of the low boiling point fraction, Triglycerin diallyl ether having two allyl groups in one molecule was prepared.

The triglycerol diallyl ether thus obtained had a viscosity of 330 mm ² / s and had a hydroxyl value of 523 KOH mg / g and a light yellow liquid having an unsaturated degree of 6.13 meq / g. The hydroxyl value and the degree of unsaturation were almost equal to the theoretical values (525, 6.24, respectively).

A tetraglycerine diallyl ether having two allyl groups in one molecule represented by the following formula (14) was prepared in the same manner as above except that diglycerin was used instead of monoglycerine. The obtained tetraglycerol diallyl ether had a viscosity of 1,397 mm ² / s, and was a pale yellow liquid having a hydroxyl value of 533 KOH mg / g and an unsaturation of 5.05 meq / g.

[Production of ABA Polyglycerin Modified Silicone]

Using the produced diallylated polyglycerol, the ABA type polyglycerol modified silicone of Nos. 1-11 shown in Table 1 was manufactured. In the production thereof, the molar ratio (SiH group / allyl group) of the allyl group of the hydrosilyl group of the α-organohydrogenpolysiloxane and the allyl group of the diallylated polyglycerol derivative is 1.0 in a reactor equipped with a stirrer, a thermometer, and a reflux tube. Diallylated polyglycerol, a solvent (isopropyl alcohol), and an effective amount of a catalyst (platinum chloride) were added to each of the α-organohydrogenpolysiloxanes shown in Table 1, followed by addition reaction, followed by addition of the reaction solution under reduced pressure. It distilled at 100 degreeC, and the solvent was distilled off and performed. In addition, in the manufactured ABA type | mold polyglycerol modified silicone No.1-11, each structural unit A is a monovalent group which lose | disappears 1 hydrogen atom from each (alpha)-organohydrogenpolysiloxane shown in Table 1, and a structure The unit B is a group represented by the following formula (15) in the case of Nos. 1 to 7 and a group represented by the following formula (16) in the case of Nos. 8 to 11.

Herein, the production of the ABA polyglycerol-modified silicone No. 3 will be described in detail. 100 g of triglycerol diallyl ether, 300 g of isopropyl alcohol, and 0.05 g of isopropyl alcohol solution of 0.5 wt% chloroplatinic acid are added thereto. 210 g of organohydrogenpolysiloxane (MD ₃ M ^H ) was added dropwise and reacted at 60 ° C. while stirring, and after heating and aging for 3 hours, the reaction mixture was distilled at 100 ° C. under reduced pressure, and isopropyl alcohol was distilled off. Thus, ABA type polyglycerol modified silicone No. 3 was produced. In the same manner, different numbers of ABA-type polyglycerine-modified silicones having different siloxane polymerization degrees and glycerin polymerization degrees were prepared.

The obtained ABA polyglycerol-modified silicone No. 3 was analyzed by ²⁹ Si-NMR with heavy chloroform as a solvent. As a result, it was found that Me ₃ SiO- group and -CH ₂ Me ₂ SiO were 1: 1 at 7.52 ppm and 7.11 ppm. Since the signal by the-group was observed and the signal by the -OMe ₂ SiO- group was observed at a ratio of 2: 1 between -21.4 ppm and -21.6 ppm, the siloxane structure was represented by the α-organohydrogenpolysiloxane (Table 1). MD ₃ M ^H ) was confirmed to be a monovalent group resulting from the loss of one hydrogen atom.

In addition, as a result of analysis by ¹ H-NMR, the integral value of the 0.1 ppm signal by the Me ₃ SiO- group and the -Me ₂ SiO- group to the integral value of 2 ppm of the 0.5 ppm signal by the -CH ₂ Me ₂ SiO- group was 33H. Therefore, it was confirmed that 1 mol of MD ₃ M ^H was bonded with respect to 1 mol of allyl groups.

Moreover, since the Me ₂ -CH ₂ signal of the polyglycerol chain which includes hydrogen of the hydroxyl group on the integrated value of 0.5 ppm 2H signal by groups SiO- (m, 3.3 to 3.9 ppm) the integral value of 11H, a polyglycerin chain It was confirmed that 2 moles of siloxane were bonded to each other.

As a result of the same analysis for the ABA-type polyglycerin-modified silicones having numbers other than No. 3, the siloxane structure is a monovalent group resulting from the loss of one hydrogen atom from each of the α-organohydrogenpolysiloxanes shown in Table 1, It was confirmed that (alpha) -organohydrogenpolysiloxane has 1 mol couple | bonded with respect to 1 mol of allyl groups, and 2 mol of siloxane couple | bonded with respect to the polyglycerol chain.

In addition, as a result of IR measurement by the KBr plate method, strong absorption by OH stretching vibration was observed around 3,400 cm ⁻¹ , and it was confirmed that the prepared ABA type polyglycerol-modified silicone No. 3 was a compound having a polyglycerol group ( See FIG. 1). Also about the ABA type polyglycerol modified silicone of numbers other than No. 3, it was confirmed that it is a compound which has a polyglycerol group.

[ABA type polyglycerol modified silicone No. 1 to 11]

Table 1 shows the results of measuring the properties of the 11 types of ABA-type polyglycerin-modified silicone.

In addition, kinematic viscosity was measured with the Canon Penske viscometer, specific gravity was measured with the buoyancy, and refractive index was measured with the Abbe refractometer, respectively.

[Checking Surface Tension Reduction Capability and Compatibility]

In order to investigate the surface tension-lowering ability of the obtained ABA-type polyglycerol modified silicone, the amount shown in Table 2 in sorbine-MP (methyl methoxypropionate, brand name, Showa Denko Co., Ltd.) used as a solvent for resists The surface tension at 25 ° C. when the above-mentioned ABA-type polyglycerine-modified silicone Nos. 1, No. 4, No. 8 and No. 10 were added (0.1 wt%, 1 wt%, 10 wt%) It was measured by a Wilhelmy type surface tension meter (manufactured by Kyowa Kaimen Kagaku Co., Ltd., a fully automatic interface tension meter CBVP-Z type).

Moreover, in order to investigate the compatibility of the ABA type | mold polyglycerol modified silicone with the resist solvent, the said ABA type | mold polyglycerol modified silicone No.1, No. 4, No. 8, in ethyl lactate used as a resist solvent 20 weight% of No. 10 was respectively added, and the solubility to ethyl lactate was visually determined. In addition, as Comparative Compound 1, fluorine polyether co-modified silicone: X-70-193 (manufactured by Shin-Etsu Chemical Co., Ltd., brand name), and Comparative Compound 2, under the same conditions using a compound represented by the following formula (17): The measurement was performed. The results are shown in Table 2.

From the result shown in Table 2, it turns out that ABA type polyglycerol modified silicone No.1, No.4, No.8, No.10 all remarkably reduce the surface tension of sorbine-MP, and provide leveling property. Could. In particular, although the polyglycerol modified silicone No. 10 did not have a fluorine functional group, it showed the surface tension reducing ability almost comparable with the comparative compound 1 which is fluoro polyether co-modified silicone which has a high surface tension lowering ability. In addition, the polyglycerol modified silicone No. 1, No. 4, No. 8, and No. 10 all had favorable compatibility with ethyl lactate.

Hereinafter, the actual resist solution was produced and the effect of the photosensitive resin composition of this invention was confirmed.

[Synthesis of novolak resin (X) substituted with 1,2-naphthoquinone diazide sulfonyl ester group]

In a three-necked flask equipped with a stirrer, a condenser and a thermometer, 75.7 g (0.7 mol) of p-cresol, 32.5 g (0.3 mol) of m-cresol, 52.3 g (0.59 mol) of 37 wt% aqueous formaldehyde solution and oxalic acid as a polycondensation catalyst 0.30 g (2.40 × 10 ⁻³ mol) of dihydrate was added thereto, the flask was immersed in an oil bath, and the polycondensation was carried out for 1 hour while maintaining the internal temperature at 100 ° C. After completion of the reaction, 500 ml of methyl isobutyl ketone was added and stirred for 30 minutes, and then the aqueous layer was separated. The product extracted in the methyl isobutyl ketone layer was washed with 300 ml of pure water five times, separated, and separated by an evaporator. The pressure reduction strip of 150 degreeC was performed at mmHg, and the novolak resin (X) (87g) of 6,200 of weight average molecular weights (Mw) was obtained.

In addition, the measurement of a weight average molecular weight uses a GPC column (made by Tosoh Corporation, G-2000H6 * 2, G-3000H6 * 1, G-4000H6 * 1), and flow volume 1.5 ml / min, elution solvent THF, It performed at the column temperature of 40 degreeC.

Subsequently, in a three-necked flask equipped with a stirrer, a dropping funnel, a condenser, and a thermometer under shading, 120 g (1 mol) of the novolak resin (X) and 26.8 g of 1,2-naphthoquinone diazide sulfonyl chloride (0.10) Mole) and 400 ml of dioxane were dissolved, and then 10.1 g (0.10 mole) of triethylamine was added dropwise so that the internal temperature did not exceed 30 ° C. Thereafter, the mixture was aged for 1 hour, poured into 5,000 ml of 0.1 N hydrochloric acid, filtered and fractionated. The precipitate was further separated and dissolved in 800 g of ethyl acetate, washed with water, separated, and stripped at 40 ° C. to remove the solvent. It dried under vacuum and obtained the 1, 2- naphthoquinone diazide sulfonyl esterified novolak resin (Y) (140g).

The obtained novolak resin (Y) confirmed from the analysis result of NMR that 10% of the hydrogen atoms of the hydroxyl group in a novolak resin are 1,2-naphthoquinone diazide sulfonyl esterification.

[Synthesis of methyl vinyl ether maleic monoalkyl ester copolymer (Z)]

In a three-necked flask equipped with a stirrer, a dropping funnel, a condenser, and a thermometer, a methylvinyl ether / maleic anhydride copolymer having a weight average molecular weight (Mw) of about 150,000 was dissolved in 100 g of Gantrez (ISP, trade name) in 4,000 g of methanol. After the reaction, the reaction was carried out at reflux at 60 to 65 ° C for about 2 hours. After the reaction, methanol was distilled off to obtain 135 g of a methylvinyl ether-maleic acid monomethyl ester copolymer (Z) having a weight average molecular weight (Mw) of about 200,000.

Example 1

10 g of novolak resin (Y) substituted with 1,2-naphthoquinone diazide sulfonyl ester group was dissolved in 40 g of ethyl lactate, followed by methylvinylether-maleic acid monomethyl having a weight average molecular weight (Mw) of about 200,000. 2 g of the ester copolymer (Z) and 0.05 g of the leveling agents shown in Table 3 as the leveling agents were mixed, dissolved, and filtered through a 0.2 µm pore membrane filter to prepare a resist solution.

Next, on the substrate on which gold was deposited by sputtering on a 6 inch silicon wafer, the resist solution was applied using a spinner at a condition of 2,000 rpm / 30 seconds, and prebaked at 120 ° C./300 seconds on a hot plate to have a thickness. A 3 탆 resist film was formed.

The film thickness distribution of the obtained resist film was measured with NanoSpec 6100 (manufactured by Nanometrics Japan Co., Ltd.) which is a film thickness measurement system. The results are shown in Table 3.

From this result, the resist film using ABA type | mold polyglycerol modified silicone showed favorable flatness (film thickness uniformity).

* ABA type polyglycerin modified silicone No. 1: 1 (weight) mixture of 4 and 5

Synthesis of Polyimide Silicone Resin

35.8 g (0.1 mol) of 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride and 300 g of n-methyl-2-pyrrolidone were placed in a flask equipped with a stirrer, a thermometer and a nitrogen replacement device. Input. Subsequently, 14.7 g (0.003 mol) of diaminosiloxane represented by the following formula (18), with an average of b: 64, and 39.8 g (0.097 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane ) Was added into the flask while adjusting the temperature of the reaction system not to exceed 50 ° C. After addition, the mixture was further stirred at room temperature for 10 hours.

Subsequently, after attaching a reflux condenser equipped with a water receiver to the flask, 30 g of xylene was added, the temperature was raised to 150 ° C, and the temperature was maintained for 6 hours, whereby a yellowish brown solution was obtained. The yellowish brown solution thus obtained was cooled to room temperature (25 ° C), and then charged in methanol to reprecipitate. The obtained precipitate was dried to obtain a polyimide silicone resin (number average molecular weight (Mn) 31,000) having a repeating unit represented by the following formula (19).

Example 2

10 g of the obtained polyimide silicone resin was dissolved in 30 g of cyclohexanone, and then 0.04 g of the leveling agent shown in Table 4 was added and mixed, followed by filtration with a 0.2 µm pore membrane filter to prepare a resist solution. In Table 4, KF-643 (manufactured by Shin-Etsu Chemical Co., Ltd.) is a polyether-modified trisiloxane, and X-70-193 (manufactured by Shin-Etsu Chemical Co., Ltd., brand name) is a fluoropolyether ball. Modified silicone.

Next, the resist solution was applied on a 6 inch silicon wafer using a spin coater under conditions of 1,500 rpm / 60 seconds, and thermally treated at 120 ° C./120 seconds on a hot plate to form a resist film having a thickness of about 9 μm.

Table 4 shows the results of measuring the film thickness distribution of the obtained resist film in NanoSpec 6100 (same as above). As can be seen from this result, the resist film using ABA-type polyglycerol modified silicone showed good flatness (film thickness uniformity).

* ABA type polyglycerin modified silicone No. 1: 1 (weight) mixture of 4 and 5

The photosensitive resin composition of this invention is excellent in compatibility with the solvent for photosensitive resin compositions, and contains (poly) glycerol modified silicone of the predetermined structure which has high surfactant activity and surface smoothing effect as a leveling agent for photosensitive resin compositions. Therefore, it is excellent in the malleability which is easy to spread on a base material, can apply | coat uniformly without generating application | coating nonuniformity, and exhibits the outstanding effect that safety is also high.

Claims (6)

0.01 to 20% by weight of (poly) glycerine-modified silicone formed by combining ABA with structural unit A, which is an organopolysiloxane residue represented by Formula 1 below, and structural unit B, which is a (poly) glycerine derivative residue represented by Formula 2 below: Photosensitive resin composition containing. <Formula 1>

<Formula 2>

[In the meal, R ¹ is, independently from each other, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group having 1 to 10 carbon atoms which may be substituted with halogen, x is an integer from 0 to 100, α is 1 or 2, R ² is independently an alkylene group having 2 to 11 carbon atoms, s is an integer from 1 to 11.] The photosensitive resin composition of Claim 1 whose structural unit B is a (poly) glycerine derivative residue represented by following General formula (3). <Formula 3>

[Wherein, R ² is a trimethylene group and s is an integer of 1 to 8] The photosensitive resin composition of Claim 1 or 2 which is a positive resist composition. The photosensitive resin composition of Claim 1 or 2 which is a negative resist composition. The board | substrate which apply | coats the photosensitive resin composition of Claim 1. The leveling agent for photosensitive resin compositions containing the (poly) glycerol modified silicone of Claim 1 as a component.

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