KR20130030221A - Positive-type photosensitive resin composition, method for forming cured film, cured film, organic el display device, and, liquid crystal display device - Google Patents

Abstract

PURPOSE: A positive type photosensitive resin composition, a cured film, an organic EL display device, and a liquid crystal display device are provided to form a uniform display panel and to have excellent resistance against NMP. CONSTITUTION: A positive type photosensitive resin composition contains copolymer 1, copolymer 2, and a photoacid generator. Copolymer 1 has a crosslinkable group and a structure unit which has a radical protected by an acid dissolution group. Copolymer 2 has a crosslinkable group and a structure unit derived from styrene. The pKa of a generated acid from the photoacid generator is 4 or less.

Description

TECHNICAL FIELD [0001] The present invention relates to a positive type photosensitive resin composition, a method of forming a cured film, a cured film, an organic EL display device, and a liquid crystal display device using the positive type photosensitive resin composition, a cured film, DISPLAY DEVICE}

The present invention relates to a positive photosensitive resin composition, a method of forming a cured film, a cured film, an organic EL display device, and a liquid crystal display device. More particularly, the present invention relates to a positive type photosensitive resin composition suitable for forming a planarizing film, a protective film, or an interlayer insulating film of an electronic component such as a liquid crystal display, an organic EL display, an integrated circuit element, And a method for forming a cured film.

In an organic EL display device, a liquid crystal display device, or the like, a patterned interlayer insulating film is provided. In forming the interlayer insulating film, a photosensitive resin composition is widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness can be obtained.

The interlayer insulating film in the display device is expected to have high transparency in addition to physical properties of a cured film such as excellent insulating property, solvent resistance, heat resistance, hardness, and indium tin oxide (ITO) sputter suitability. For this reason, it has been tried to use an acrylic resin excellent in transparency as a film forming component.

As a conventional photosensitive resin composition for an interlayer insulating film, for example, Patent Documents 1 and 2 disclose a chemically amplified radiation-sensitive resin composition containing an acetal structure and a resin containing an epoxy group or a crosslinkable group, Lt; / RTI >

Japanese Patent Application Laid-Open No. 2004-264623 Japanese Patent Application Laid-Open No. 2009-098616

2. Description of the Related Art In recent years, in the field of electronic materials, the circuit resistance and the capacity of capacitors between wirings have increased with progress of high integration, multifunctionalization, and high performance, resulting in increase of power consumption and delay time. Among them, the increase of the delay time is a factor of the decrease of the signal speed of the device and the generation of the crosstalk. Therefore, in order to reduce the delay time and speed up the device, reduction of the parasitic capacitance is required. In order to reduce the parasitic capacitance, a demand for lowering the dielectric constant of the interlayer insulating film is increasing. The interlayer insulating film made of an acrylic resin is lower than that of a silicon nitride film (SiN, relative dielectric constant of about 8), a silicon oxynitride film (SiON, relative dielectric constant of about 4.5), a silicon oxide film (SiO 2, relative dielectric constant of about 4) In addition, low dielectric constant is expected.

As a method of lowering the dielectric constant of the interlayer insulating film, there is known a method of adding a styrene-containing polymer to a photosensitive resin composition. However, adding such a hydrophobic polymer has a demerit of lowering the sensitivity, Degradation was a problem.

Further, the present inventors have found that the addition of the styrene-containing polymer to the photosensitive resin composition deteriorates the resistance to NMP (N-methylpyrrolidone) used in the alignment film laminating process. In addition, when the resistance to NMP is poor, it is clear that panel display irregularity tends to occur in the panel reliability test.

In the conventional knowledge, it is difficult to lower the dielectric constant of the insulating film and satisfy all of the sensitivity and resistance to NMP.

The present invention is directed to solving the above problems.

That is, a problem to be solved by the present invention is to provide a positive film having a high sensitivity, a cured film having a low dielectric constant, good resistance to NMP (N-methylpyrrolidone) and suppressing occurrence of panel display unevenness in a reliability test A cured film using the photosensitive resin composition and a method of forming the same, and an organic EL display device and a liquid crystal display device provided with the cured film.

The above problem of the present invention has been solved by the means described in the following <1>, <9>, <11>, <13> or <14>. Are described below along with <2> to <8>, <10>, and <12> which are preferred embodiments.

(Component B) a copolymer having at least (a1) a structural unit having a carboxyl group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group, (Component B) , (B2) a copolymer having a constituent unit having a crosslinkable group, and (C) a photoacid generator having a pKa of not more than 4 in the generated acid,

(2) The I / O value obtained by dividing the inorganic value (I) based on the organic conceptual diagram of the component B by the organic value (O) and the I / O value of the copolymer A in which the carboxyl group of the component A is protected with an acid- A positive photosensitive resin composition according to < 1 >, wherein the difference in I / O value is 0.40 or less,

<3> The positive photosensitive resin composition according to <1> or <2>, wherein the (a1) acid-decomposable group in the structural unit having a carboxyl group protected residue with an acid-decomposable group is acetal,

<4> The positive photosensitive resin composition according to any one of <1> to <3>, wherein the component A is a (meth) acrylic copolymer.

<5> The positive photosensitive resin composition according to any one of <1> to <4>, wherein the component C is an oxime sulfonate compound having at least one of oxime sulfonate residues represented by formula (c0)

(In the formula (c0), the broken line indicates a bonding site)

<6> The compound according to any one of <1> to <5>, wherein the component C is a compound represented by the formula (OS-3), formula (OS-4), formula (OS- , A positive photosensitive resin composition described in &

Wherein R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ² independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ¹ represents an alkyl group, an aryl group or a heteroaryl group, ⁶ represents independently a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, and m represents 0 to 6 Lt; / RTI &gt;

(In the formula (c3), R ^B1 represents an alkyl group, an alkoxy group, or a halogen atom, and R ^B2 represents an alkyl group or an aryl group)

The positive photosensitive resin composition according to any one of < 1 > to < 6 >, further comprising a block isocyanate compound,

<8> The positive photosensitive resin composition according to any one of <1> to <7>, further containing an alkoxymethyl group-containing crosslinking agent,

(1) a coating step of applying the positive-working photosensitive resin composition described in any one of <1> to <8> on a substrate; (2) an exposure step of exposing the applied photosensitive resin composition by actinic light; , (3) a developing step of developing the exposed photosensitive resin composition with an aqueous developing solution, and (4) a post-baking step of thermally curing the developed photosensitive resin composition,

<10> The method for forming a cured film according to <9>, which comprises a step of exposing the developed photosensitive resin composition to the whole surface after the development step and before the post-baking step,

<11> A cured film formed by the method described in <9> or <10>

<12> The cured film according to <11>, which is an interlayer insulating film,

<13> An organic EL display device comprising the cured film according to <11> or <12>

<14> A liquid crystal display device comprising the cured film according to <11> or <12>.

INDUSTRIAL APPLICABILITY According to the present invention, there can be provided a positive photosensitive resin composition which has a high sensitivity, a cured film obtained has a low dielectric constant, a good resistance to NMP (N-methylpyrrolidone) A cured film using the photosensitive resin composition and a method of forming the same, and an organic EL display device and a liquid crystal display device provided with the cured film.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a conceptual diagram showing an example of an organic EL display device. Fig. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarization film 4.
2 is a conceptual diagram showing an example of a liquid crystal display device. Sectional view of an active matrix substrate in a liquid crystal display device and has a cured film 17 as an interlayer insulating film.

Hereinafter, the present invention will be described in detail.

In the specification, the description of "lower limit to upper limit" indicates "lower limit and upper limit" and "upper limit to lower limit" indicates "upper limit and lower limit". That is, a numerical range including an upper limit and a lower limit.

Also, the term "(Component A)" is a copolymer having at least (a1) a structural unit having a carboxyl group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group " "(A1) a structural unit having a carboxyl group protected with an acid-decomposable group" and the like are also simply referred to as "structural unit (a1)".

The term "(meth) acrylate" refers to both of "acrylate" and "methacrylate", and "(meth) acrylate" &Quot;, respectively.

(Positive photosensitive resin composition)

The positive photosensitive resin composition of the present invention (hereinafter also simply referred to as &quot; photosensitive resin composition &quot;) is a composition comprising a constituent unit (component A) comprising at least (a1) a constituent unit in which a carboxyl group is protected by an acid- (Component B) a copolymer having at least (b1) a structural unit derived from styrene and (b2) a structural unit having a crosslinkable group, and (component C) a copolymer having a pKa of 4 or less.

The photosensitive resin composition of the present invention is excellent in sensitivity because it contains two components (component A and component B) of a specific copolymer (hereinafter also referred to as a specific resin) and a photoacid generator. Further, since the photosensitive resin composition of the present invention contains the specific two components of the resin and the photoacid generator, the resulting cured film has a low dielectric constant, so that no panel crosstalk occurs, and NMP (N-methylpyrrolidone ) Is good and a cured film in which the occurrence of panel display irregularity is suppressed in the reliability test can be formed.

The term &quot; panel crosstalk &quot; refers to a phenomenon in which a drive signal leaks to a circuit that is not driven on the panel to cause a discharge.

The photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).

The photosensitive resin composition of the present invention preferably contains an oxime sulfonate compound as a photoacid generator. However, the oxime sulfonate compound is preferably used as a catalyst for deprotection of an acidic group protected by an acid generated in response to an actinic ray Therefore, the acid generated by the action of one photon contributes to a large number of deprotection reactions, resulting in a quantum yield of more than 1, for example, a large value such as 10, and as a result of so- High sensitivity is obtained.

In the positive photosensitive resin composition of the present invention, the I / O value obtained by dividing the inorganic value (I) based on the organic concept diagram of the component B by the organic value (O) and the I / O value obtained by dividing the carboxyl value of the component A by the acid decomposable group It is preferable that the difference in I / O value of the copolymer in which all of the residues are deprotected is 0.40 or less. It is preferable that the difference between the I / O value of the component A and the component B is 0.40 or less, because the effect of the present invention is further exerted.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The method of introducing the constituent unit contained in the copolymer such as the component A or the component B used in the present invention may be a polymerization method or a polymer reaction method. As the polymerization method, monomers containing a predetermined functional group are synthesized in advance, and these monomers are copolymerized. In the polymer reaction method, a necessary functional group is introduced into the constituent unit by using a reactive group contained in the constituent unit of the obtained copolymer after the polymerization reaction. Examples of the functional group include a protecting group for protecting an acid group such as a carboxyl group or a phenolic hydroxyl group and for decomposing in the presence of a strong acid, a crosslinking group such as an epoxy group or an oxetanyl group, a crosslinking group such as a phenolic hydroxyl group or a carboxyl group Alkali-soluble groups (acid groups), and the like.

(Component A) A copolymer comprising at least (a1) a structural unit having a carboxyl group protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group

The positive-working photosensitive resin composition of the present invention is a positive-type photosensitive resin composition comprising (A) at least (a1) a structural unit having a carboxyl group protected by an acid-decomposable group (hereinafter also referred to as a structural unit (a1)) and (a2) (Hereinafter also referred to as &quot; structural unit (a2) &quot;).

The constituent unit (a1) and the constituent unit (a2) may be the same constituent unit, but are preferably different constituent units.

Component A is preferably an alkali-insoluble resin that becomes alkali-soluble when the acid-decomposable group decomposes. Here, the "acid-decomposable group" means a functional group decomposable in the presence of an acid. The term "alkali solubility" refers to a property of a coating film (thickness 3 μm) formed by applying a solution of a compound (resin) on a substrate and heating at 90 ° C. for 2 minutes at 0.4% by weight of tetramethylammonium hydroxide Means that the dissolution rate in the aqueous solution of the lockside is 0.01 탆 / second or more. On the other hand, "alkali insoluble" means that the dissolution rate is less than 0.01 μm / sec. It is more preferable that the alkali dissolution rate of the component A is less than 0.005 탆 / sec.

The component A is preferably an addition polymerization type resin, more preferably a polymer comprising a constituent unit derived from (meth) acrylic acid and / or an ester thereof. The component A may have a constituent unit other than the constituent unit derived from (meth) acrylic acid and / or an ester thereof, for example, a constituent unit derived from a vinyl compound, and the like. do not include.

The component A preferably contains 50 mol% or more, more preferably 80 mol% or more, and more preferably 90 mol% or more of monomer units derived from (meth) acrylic acid and / Or more, and particularly preferably 100 mol% or less.

The method of introducing the constituent unit contained in the component A may be either a polymerization method or a polymer reaction method, and these two methods may be used in combination.

As the polymerization method, for example, an ethylenically unsaturated compound having a carboxyl group protected by an acid-decomposable group, an ethylenically unsaturated compound having a crosslinkable group, and an ethylenically unsaturated compound having an acid such as a carboxyl group, Followed by polymerization to obtain a desired copolymer.

As a polymer reaction method, epichlorohydrin may be reacted with a copolymer of 2-hydroxyethyl methacrylate to introduce an epoxy group. As described above, after the ethylenically unsaturated compound having a reactive group is copolymerized, a reactive group remaining on the side chain is utilized to form a functional group such as a residue protected with an acid-decomposable group by a phenolic hydroxyl group or a carboxyl group and / Can be introduced into the side chain.

&Lt; Structural unit (a1) >

Component A contains at least (a1) a constituent unit in which the carboxyl group has a moiety protected with an acid-decomposable group. When the component A has the constituent unit (a1), a highly sensitive photosensitive resin composition can be obtained.

The "residue in which the carboxyl group is protected with an acid-decomposable group" in the present invention is preferably a residue in which the carboxyl group is protected with an acetal, a ketal, a tertiary alkyl group, or a tertiary alkylcarbonate group.

As the acid decomposable group, known ones can be used as the acid decomposable group in the positive resist for KrF and the positive resist for ArF, and there is no particular limitation. Examples of the acid decomposable group include groups which are relatively easily decomposable by an acid (e.g., acetal functional groups such as tetrahydropyranyl group and ethoxyethyl group) and groups which are relatively difficult to decompose by an acid (for example, t-butyl Butyl group-containing functional groups such as an ester group and a t-butyl carbonate group) are known. As the structural unit (a1), a structural unit having a carboxy group as an acetal or a ketal-protected residue is preferable from the viewpoint of sensitivity.

When the carboxy group is an acetal or ketal-protected residue represented by the following formula (A1), the moiety has a structure of -C (= O) -O-CR ¹ R ² (OR ³ ) as a whole.

(Formula (A1) of, R ¹ and R ² are, each independently represents a hydrogen atom, alkyl group, or an aryl group, and either one of at least R ¹ and R ² alkyl group, or aryl group, R ³ is Or an aryl group, and R ¹ or R ² and R ³ may be connected to form a cyclic ether. Further, the broken line portion in the formula (A1) represents a bonding position with another structure)

In the formula (A1), the alkyl group in R ¹ , R ² and R ³ may be any of linear, branched or cyclic.

The straight chain or branched chain alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec- Butyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group and n-decyl group. Among them, a methyl group and an ethyl group are preferable.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group and an isobornyl group. Of these, monocyclic ones are preferable, and cyclohexyl groups are more preferable.

The alkyl group may have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an aryl group having 6 to 20 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. When R ¹ , R ² and R ³ are a haloalkyl group and have an aryl group as a substituent, R ¹ , R ² and R ³ are an aralkyl group when they have a halogen atom as a substituent. As the aralkyl group, a benzyl group is preferable.

In the formula (A1), the aryl group in R ¹ , R ² and R ³ preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and as the substituent, an alkyl group having 1 to 6 carbon atoms can be preferably exemplified. As the aryl group, for example, a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a 1-naphthyl group and the like can be mentioned, and a phenyl group is preferable.

In formula (A1), R ¹ , R ² and R ³ may be bonded to each other to form a ring with the carbon atom to which they are bonded. Examples of the ring structure when R ¹ and R ² , R ¹ and R ³ or R ² and R ³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group , An adamantyl group, and a tetrahydropyranyl group.

In formula (A1), it is preferable that either one of R ¹ and R ² is a hydrogen atom or a methyl group.

As the radically polymerizable monomer used for forming the constituent unit having a moiety represented by the formula (A1), a commercially available one may be used. For example, the method described in paragraphs 0025 to 0026 of Japanese Patent Application Laid-Open No. 2009-098616 , Or a compound synthesized by a known method may be used.

As the structural unit (a1), a structural unit represented by the formula (A2) is more preferable.

(In the formula (A2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group or an aryl group , R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group)

Formula (A2) of, R ¹ ~ R ³ are, the same formula and R ¹ ~ R ³ in (A1), as a preferred range.

In the formula (A2), R ¹ and R ² are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. R ³ is preferably a straight chain, branched chain or cyclic alkyl group having 6 or less carbon atoms or an aralkyl group having 7 to 10 carbon atoms, more preferably an ethyl group, a cyclohexyl group or a benzyl group. As the cyclic ether to which R ¹ or R ² and R ³ are connected, a tetrahydropyranyl group or a tetrahydrofuranyl group is preferable. R ⁴ is preferably a methyl group. X is preferably a single bond or a phenylene group.

As specific preferred examples of the structural unit (a1), the following structural units can be exemplified. R represents a hydrogen atom or a methyl group.

The constituent unit (a1) may be a constituent unit in which the carboxyl group has a residue protected by a tertiary alkyl group represented by the formula (A3). Compared with the acetal or ketal protected residue, the sensitivity is lower, but it is preferable from the viewpoint of excellent storage stability. When the carboxy group is a residue protected with a tertiary alkyl group represented by the formula (A3), the moiety has a structure of -C (= O) -O-CR ¹ R ² R ^{3 as} a whole.

In formula (A3), R ¹ , R ² and R ³ each independently represent an alkyl group or an aryl group, and any two of R ¹ , R ² and R ³ may be bonded to each other to form a ring. The broken line part in the formula (A3) represents a bonding position with another structure. Specific examples of the alkyl group and the aryl group in R ¹ to R ³ in the formula (A3) are the same as the specific examples of the alkyl group and the aryl group in the formula (A1).

In the formula (A3), a preferable example is a combination of R ¹ = R ² = R ³ = methyl group, a combination of R ¹ = R ² = methyl group and R ³ = benzyl group.

Among them, the structural unit (a1) is preferably a structural unit represented by the following formula (a1-1) from the viewpoint of sensitivity.

(In formula (a1-1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 6 carbon atoms, R ³ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms , And R ² and R ³ may be connected to form a ring)

In the formula (a1-1), it is preferable that R ¹ is a methyl group.

In formula (a1-1), R ² is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

In formula (a1-1), R ³ is preferably an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms, more preferably an ethyl group or a cyclohexyl group.

In the formula (a1-1), when R ² and R ³ are connected to form a ring, the group to which R ² and R ³ are connected is preferably an alkylene group having 3 to 6 carbon atoms, and 1,3-propylene Or a 1,4-butylene group.

&Lt; Structural unit (a2) >

Component A has at least (a2) a structural unit having a crosslinkable group.

As the crosslinkable group, any of those which form a covalent bond by reacting with the above-mentioned carboxyl group, and those which form a covalent bond by the action of heat or light between the crosslinkable groups.

As the structural unit (a2) having a crosslinkable group which reacts with a carboxyl group to form a covalent bond, a structural unit having an epoxy group or an oxetanyl group and a structural unit having an N-alkoxymethylamide group are preferable, Carbon-carbon double bond is preferable as a covalent bond formed by the action. Among these crosslinkable groups, it is preferable to react with a carboxyl group to form a covalent bond.

The crosslinkable group is preferably a structural unit having an epoxy group or an oxetanyl group and contained in the component A. As the structural unit (a2), both groups of an epoxy group and an oxetanyl group may be contained.

The structural unit having an epoxy group or an oxetanyl group is preferably a structural unit having an alicyclic epoxy group or an oxetanyl group, more preferably a structural unit having an oxetanyl group.

The alicyclic epoxy group is a group in which an aliphatic ring and an epoxy ring form a condensed ring, and specific examples thereof include 3,4-epoxycyclohexyl group, 2,3-epoxycyclohexyl group, 2,3-epoxycyclopentyl group And the like.

The group having an oxetanyl group is not particularly limited as long as it has an oxetanyl ring, but a (3-ethyloxetan-3-yl) methyl group can be preferably exemplified.

The constituent unit having an epoxy group or an oxetanyl group may have at least one epoxy group or oxetanyl group in one constituent unit and may include at least one epoxy group and at least one oxetanyl group and two or more epoxy groups, Or may have two or more oxetanyl groups, and it is not particularly limited, but it is preferable that a total of 1 to 3 epoxy groups and oxetanyl groups are present, more preferably 1 or 2 epoxy groups and oxetanyl groups in total , And more preferably one epoxy group and oxetanyl group.

Specific examples of the radically polymerizable monomer used to form the structural unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -Propyl acrylate Epoxycyclohexyl methacrylate, glycidyl acrylate, glycidyl? -N-butyl acrylate,? -Epoxybutyl acrylate,? -Epoxybutyl methacrylate, Epoxy heptyl,? -Ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, paragraph 413 And compounds containing an alicyclic epoxy skeleton as described in [0035].

Examples of the radical polymerizable monomer used for forming the oxetanyl group-containing structural unit include (meta) acrylic acid esters having an oxetanyl group described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2001-330953 .

As examples of the radical polymerizable monomer used for forming the constituent unit having an epoxy group or an oxetanyl group, a monomer containing a methacrylic acid ester structure or a monomer containing an acrylic ester structure is preferable.

Among these radical polymerizable monomers, more preferred are compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and oxeta compounds described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2001-330953 (Meth) acrylic acid ester having an oxetanyl group as described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2001-330953, and particularly preferred is a (meth) acrylic acid ester having an oxetanyl group. Among these, preferred are acrylic esters such as 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, methyl (3-ethyloxetan-3-yl) (3-ethyloxetan-3-yl) methyl, and methacrylic acid (3-ethyloxetan-3-yl) methyl. These constituent units may be used singly or in combination of two or more.

As specific preferred examples of the structural unit (a2), the following structural units can be exemplified.

As the crosslinkable group, an amide in which an alkoxymethyl group is substituted with a nitrogen atom is preferably used. As the constituent unit having an amide group in which the alkoxymethyl group is substituted with a nitrogen atom, a constituent unit represented by the following formula (A4) is preferable.

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms)

In formula (A4), R ¹ represents a hydrogen atom or a methyl group, preferably a hydrogen atom. R ² represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The alkyl group or aryl group may be substituted. Examples of the substituent include a halogen atom, a hydroxyl group, an amino group, a nitro group and a cyano group. As R ² , a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group and an s-butyl group are more preferable. R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the alkyl or aryl group may be substituted. Examples of the substituent include a halogen atom, a hydroxyl group, an amino group, a nitro group, Alkoxy group having 1 to 20 carbon atoms. R ³ is more preferably a hydrogen atom or an alkoxymethyl group having 1 to 20 carbon atoms.

Examples of the radical polymerizable monomer used for forming the constituent unit represented by the formula (A4) include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, Nn-butoxymethyl (Meth) acrylamide and N-butoxymethyl (meth) acrylamide are preferable, and Nn-butoxymethyl (meth) acrylamide and Ni-butoxymethyl Acrylamide is particularly preferred.

Examples of commercially available products of these compounds include NMMA, NEMA, NBMA, IBMA, NMMM, NEMM, NBMM, and IBMM manufactured by NRC Unitech Co.,

As specific preferred examples of the structural unit (a2), the following structural units can be exemplified.

From the viewpoint of the sensitivity, the content of the monomer unit constituting the constituent unit (a1) in the component A is preferably from 10 to 70 mol%, more preferably from 15 to 65 mol%, based on all the monomer units constituting the component A. [ , And more preferably 20 to 60 mol%.

From the viewpoint of resistance to NMP, the content of the monomer unit forming the constituent unit (a2) in the component A is preferably from 10 to 70 mol%, more preferably from 10 to 70 mol%, based on all the monomer units constituting the component A. [ , More preferably 60 mol%, and still more preferably 10 mol% to 50 mol%.

&Lt; Other structural unit (a3) >

Component A may further contain other structural units (a3) within the range not to impair the effects of the present invention.

Examples of the radical polymerizable monomer used for forming the constituent unit (a3) include the compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623 (provided that the above-mentioned constituent unit (a1) And (a2) are excluded).

From the viewpoint of sensitivity, it is preferable that the component A further has a structural unit having an acid group as the structural unit (a3).

As the acid group, a structural unit having a carboxyl group and / or a phenolic hydroxyl group is more preferable, and a structural unit having a carboxyl group is more preferable.

The structural unit (a3) is more preferably a structural unit derived from acrylic acid or methacrylic acid, particularly preferably a structural unit derived from methacrylic acid.

Preferable examples of the structural unit (a3) include structural units derived from at least one kind selected from the group consisting of (meth) acrylic acid esters, hydroxyl group-containing unsaturated carboxylic acid esters, alicyclic structure-containing unsaturated carboxylic acid esters, and N-substituted maleimides .

More preferred examples include (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan- (Meth) acrylic acid esters having an alicyclic structure such as isobornyl, cyclohexyl (meth) acrylate and 2-methylcyclohexyl (meth) acrylate, hydroxyl group-containing unsaturated carboxylic acid esters such as 2-hydroxyethyl (meth) N-substituted maleimide and the like.

As the structural unit (a3), methacrylic acid or a structural unit derived from 2-hydroxyethyl methacrylate is more preferable.

These structural units (a3) may be used alone or in combination of two or more.

The content of the monomer unit constituting the constituent unit (a3) in the case of containing the constituent unit (a3) among all the monomer units constituting the component A is preferably from 1 to 50 mol%, more preferably from 5 to 40 mol% %, And particularly preferably from 5 to 30 mol%.

The weight average molecular weight of the component A in the present invention is preferably from 2,000 to 100,000, more preferably from 3,000 to 50,000, even more preferably from 4,000 to 30,000, and particularly preferably from 5,000 to 20,000. The weight average molecular weight in the present invention is preferably a polystyrene reduced weight average molecular weight determined by gel permeation chromatography (GPC) when tetrahydrofuran (THF) is used as a solvent.

The content of the component A in the photosensitive resin composition of the present invention is preferably 20 to 99% by weight, more preferably 30 to 95% by weight, more preferably 30 to 90% by weight based on the total solid content of the photosensitive resin composition. Is more preferable. The solid content of the photosensitive resin composition means an amount excluding volatile components such as a solvent.

(Component B) A copolymer having at least (b1) a structural unit derived from styrene and (b2) a structural unit having a crosslinkable group

The positive photosensitive resin composition of the present invention contains, in addition to the component A, a copolymer having (B1) at least (b1) a constituent unit derived from a styrene and (b2) a constituent unit having a crosslinkable group.

The constituent unit (b1) and the constituent unit (b2) may be the same constituent unit, but are preferably different constituent units.

Component B is preferably alkali-soluble.

The component B is preferably an addition polymerizable type resin, more preferably a copolymer containing a constituent unit derived from (meth) acrylic acid and / or an ester thereof in the constituent unit (b1). The component B may further comprise constituent units other than the constituent unit derived from the constituent unit (b1) and (meth) acrylic acid and / or the ester thereof, for example, a constituent unit derived from a vinyl compound.

The component B preferably contains the structural unit (b1) in an amount of 5 to 60 mol%, more preferably 10 to 50 mol%, and still more preferably 20 to 40 mol%, based on all the monomer units.

The component B preferably contains 50 mol% or more, more preferably 50 to 90 mol%, and most preferably 60 to 90 mol% of monomer units derived from (meth) acrylic acid and / Mol%.

The method of introducing the constituent unit contained in the component B may be either a polymerization method like the component A, a polymer reaction method, or a combination of these two methods.

&Lt; Construction unit (b1) >

Component B has (b1) a structural unit derived from a styrene.

By containing the component B having the constituent unit (b1), the dielectric constant of the interlayer insulating film obtained by curing the photosensitive resin composition of the present invention is reduced.

The structural unit (b1) is preferably a structural unit derived from a styrene represented by the following formula (b1-1). The styrene may have a substituent at the? -Position of the unsaturated group of the styrene or the benzene ring.

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ² represents a halogen atom, an amino group, a nitro group, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 6 to 12 carbon atoms An aryl group, and m represents an integer of 0 to 5)

In formula (b1-1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group.

In formula (b1-1), R ² represents a halogen atom, an amino group, a nitro group, a cyano group, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms. As the halogen atom, a fluorine atom, a chlorine atom, or a bromine atom is preferable. The amino group may be substituted, and examples of the substituent include an alkyl group having 1 to 4 carbon atoms and an aryl group having 6 to 12 carbon atoms. The alkyl group having 1 to 12 carbon atoms may be linear, branched or cyclic or may be substituted. Examples of the substituent include a halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group and an aryl group having 6 to 10 carbon atoms. The aryl group having 6 to 12 carbon atoms may be substituted, and examples of the substituent include a halogen atom, an amino group, a nitro group, a cyano group, and an alkyl group having 1 to 4 carbon atoms.

In the formula (b1-1), m represents an integer of 0 to 5, and m is more preferably 0.

Preferable examples of the structural unit derived from styrene or substituted styrene represented by the formula (b1-1) include the following structural units. Among them, a structural unit derived from styrene or? -Methylstyrene is more preferable, and a structural unit derived from styrene is more preferable.

&Lt; Construction unit (b2) >

Component B contains (b2) a structural unit having a crosslinkable group.

As the crosslinkable group, any of those which form a covalent bond by reacting with the above-mentioned carboxyl group, and those which form a covalent bond by the action of heat or light between the crosslinkable groups.

The constituent unit (b2) in the component B is in agreement with the constituent unit (a2) in the component A, and the preferable embodiment is also the same.

From the viewpoint of the relative dielectric constant, the content of the monomer unit constituting the constituent unit (b1) in the component B is preferably 5 to 50 mol%, more preferably 5 to 45 mol% with respect to all the monomer units constituting the component B , More preferably from 5 to 40 mol%.

From the viewpoint of resistance to NMP, the content of the monomer unit constituting the constituent unit (b2) in the component B is preferably from 5 to 60 mol%, more preferably from 10 to 60 mol%, based on all the monomer units constituting the constituent B. [ , More preferably 50 mol%, and still more preferably 20 mol% to 50 mol%.

&Lt; Other structural unit (b3) >

The component B may further contain other structural unit (b3) within the range not to impair the effect of the present invention.

Examples of the radical polymerizable monomer used for forming the constituent unit (b3) include the compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623 (provided that the above-mentioned constituent unit (b1) And (b2)).

From the viewpoint of sensitivity, the component B preferably has a structural unit having an acid group as the structural unit (b3) as in the structural unit (a3).

As the acid group, a structural unit having a carboxyl group and / or a phenolic hydroxyl group is more preferable, and a structural unit having a carboxyl group is more preferable. More preferably a structural unit derived from acrylic acid or methacrylic acid, and particularly preferably a structural unit derived from methacrylic acid.

As other examples of the structural unit (b3), structural units derived from at least one member selected from the group consisting of (meth) acrylic acid esters, vinyl compounds and N-substituted maleimides are preferably used.

Among them, examples of the radically polymerizable monomer used for forming the structural unit (b3) include dicyclopentanyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan- (Meth) acrylic acid esters having an alicyclic structure such as cyclohexyl acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, methyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.

The structural unit (b3) may be used alone or in combination of two or more.

The content of the monomer unit constituting the constituent unit (b3) in the case where the constituent unit (b3) is contained among all the monomer units constituting the component B is preferably 5 to 70 mol%, more preferably 15 to 65 mol% , More preferably from 20 to 60 mol%.

The weight average molecular weight of the component B in the present invention is preferably from 2,000 to 100,000, more preferably from 3,000 to 50,000, even more preferably from 4,000 to 30,000, and particularly preferably from 10,000 to 20,000. The weight average molecular weight in the present invention is preferably a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) when tetrahydrofuran (THF) is used as a solvent.

The content of the component B in the photosensitive resin composition of the present invention is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, and more preferably 10 to 30% by weight based on the total solid content of the photosensitive resin composition. Is more preferable.

The content ratio of the component A to the component B in the photosensitive resin composition of the present invention is preferably from 1 to 6 (content of component A) / (content of component B), more preferably from 2 to 6 , More preferably from 3 to 5. Within the above range, the effect of the present invention can be exerted more.

In the photosensitive resin composition of the present invention, resins other than the component A and the component B may be used in combination as long as the effect of the present invention is not impaired. It is preferable that the content of the resin other than the component A and the component B is smaller than the content of the component A and the content of the component B from the viewpoint of developability.

<I / O value>

In the photosensitive resin composition of the present invention, the I / O value obtained by dividing the inorganic value (I) based on the organic concept (O) based on the organic conceptual diagram of the component B and the I / O value obtained by dividing the carboxyl group of the component A by the acid- It is preferable that the difference in I / O value of the all-deprotected copolymer is 0.40 or less. It is preferable that the difference between the I / O value of the component A and the component B is 0.40 or less, because the effect of the present invention is further exerted.

Here, the I / O value is a value obtained by treating the polarity of various organic compounds, also called an inorganic value / organic value, organic conceptually, and is one of the functional group contributing methods for setting parameters for each functional group.

As for the I / O value, an organic concept (Koyasu Yoshio, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, paragraphs 1 to 16 (1954); Area of Chemistry, Vol. 11, No. 10, pp. 719-725 (1957); Friggs Journal, No. 34, 97-111 (1979); Friggs Journal, No. 50, 79-82 (1981); And the like.

The concept of the I / O value is that the property of a compound is divided into an organic group exhibiting covalent bonding property and an inorganic group exhibiting ionic bonding property and being positioned at one point on the direct coordinate basis in which all organic compounds are named as an organic axis and an inorganic axis .

The inorganic value is obtained by quantifying the magnitude of the influence of various substituents or bonds of the organic compound on the boiling point based on the hydroxyl group. Concretely, when the distance between the boiling curve of the straight chain alcohol and the boiling curve of the linear paraffin is about 100 ° C, the influence of one hydroxyl group is set to 100 as a numerical value. Based on this numerical value, various substituents Or a value obtained by quantifying the influence of various bonds on the boiling point is an inorganic value of a substituent contained in the organic compound. For example, the inorganic value of the -COOH group is 150, and the inorganic value of the carbon-carbon double bond is 2. Therefore, the inorganic value of any kind of organic compound means the sum of inorganic values such as various substituents and bonds possessed by the compound.

The organic value is determined based on the influence of the carbon atom representing the methylene group on the boiling point, with the methylene group in the molecule as a unit. That is, since the average value of the boiling point rise due to the addition of one carbon at about 5 to 10 carbons of the linear saturated hydrocarbon compound is 20 ° C, the organic value of one carbon atom is set to 20 based on this, and based on this, The value obtained by quantifying the influence on the boiling point of the compound or the bond is an organic value. For example, the organic value of the nitro group (-NO ₂ ) is 70.

The closer to 0 the I / O value is, the more the organic compound is nonpolar (hydrophobic and organic). The larger the value, the more polar (hydrophilic and inorganic) the organic compound.

Hereinafter, an example of a method of calculating the I / O value will be described.

The I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer (copolymerization molar ratio: 2/5/3) was calculated from the inorganic value and the organic value of the copolymer by the following method, .

I / O value = (inorganic value of copolymer) / (organic value of copolymer)

The inorganic value of the copolymer is preferably such that an inorganic value of (methacrylic acid) x (a molar ratio of methacrylic acid), (an inorganic value of methyl methacrylate) x (a molar ratio of methyl methacrylate) Value of styrene) x (molar ratio of styrene).

Since the methacrylic acid has one carboxyl group, the methacrylic acid has one ester group, and the styrene has one aromatic ring, the inorganic value of the methacrylic acid is 150 (inorganic value of the carboxyl group) x 1 (Inorganic number of ester group) x 1 (number of ester groups) = 60, and the inorganic value of styrene is 15 (inorganic value of aromatic ring) x 1 (number of aromatic rings) = 15.

Accordingly, the inorganic value of the copolymer is 645 in terms of a molar ratio of 150 x 2 (molar ratio of methacrylic acid) + 60 x 5 (molar ratio of methyl methacrylate) + 15 x 3 (molar ratio of styrene).

The organic value of the copolymer was determined from the following formula: (organic value of methacrylic acid) x (molar ratio of methacrylic acid), (organic value of methyl methacrylate) x (molar ratio of methyl methacrylate) Value) x (molar ratio of styrene).

Since the methacrylic acid has 4 carbon atoms, the methyl methacrylate has 5 carbon atoms, and the styrene has 8 carbon atoms, the organic value of the methacrylic acid is 20 (the organic value of the carbon atom) x The organic value of the styrene is 20 (the number of carbon atoms) = 80, the organic value of the methyl methacrylate is 20 (the organic value of the carbon atoms) x 5 (the number of carbon atoms) = 100, Value) x 8 (number of carbon atoms) = 160.

Accordingly, the organic value of the copolymer is 1140 in terms of 80 × 2 (molar ratio of methacrylic acid) + 100 × 5 (molar ratio of methyl methacrylate) + 160 × 3 (molar ratio of styrene).

From the above, the I / O value of the methacrylic acid / methyl methacrylate / styrene copolymer is 645 (inorganic value of the copolymer) / 1140 (organic value of the copolymer) = 0.566.

As such, there is a close relationship between the I / O value and the composition ratio of the monomers constituting the resin.

The I / O value in the present specification is a value calculated by the above-described calculation method.

As a method for controlling the I / O value represented by the component A or the component B, for example, the I / O value can be increased by increasing the ratio of the group having a large inorganic value such as a hydroxyethyl group or a hydroxypropyl group in the resin And the I / O value can be lowered by increasing the proportion of the group having a large organic value such as a dicyclopentanyl group or a dodecyl group in the resin.

(Component C) a photoacid generator having a pKa of the generated acid of 4 or less

The photosensitive resin composition of the present invention contains (C) a photoacid generator having a pKa of 4 or less in the generated acid.

The component C is preferably a compound which generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm, but is not limited to the chemical structure thereof. In the case of a photoacid generator that does not directly react with an actinic ray having a wavelength of 300 nm or more, it is preferable to use a compound that generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or more by being used in combination with a sensitizer, Can be used.

As the component C, a photoacid generator having a pKa of 4 or less of the generated acid is preferable, and a photoacid generator that generates an acid having a pKa of 3 or less is more preferable.

Further, the value of pKa can be obtained by a known measurement method, a known calculation method, and / or a literature value.

Examples of the photoacid generator having a pKa of the generated acid of 4 or less include trichloromethyl-s-triazine, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, Sulfonate compounds and the like. Of these, oxime sulfonate compounds are preferably used from the viewpoint of sensitivity. These photoacid generators may be used alone or in combination of two or more.

Specific examples thereof include the following.

As trichloromethyl-s-triazines, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) Triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan- (4,6-trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, or 2- (4-methylphenyl) ethenyl] -bis Naphthyl) -bis (4,6-trichloromethyl) -s-triazine and the like.

As the diaryl iodonium salts, diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethane sulfonate, 4-methoxyphenylphenyl iodonium trifluoromethane sulfonate, 4-methoxy (2'-hydroxy-1'-tetradecarboxy) phenyl iodonium trifluoromethanesulfonate, phenyl 4- (2'-hydroxy-1'- -Tetradecaoxy) phenyl iodonium hexafluoroantimonate, or phenyl-4- (2'-hydroxy-1'-tetradecaoxy) phenyl iodonium p-toluenesulfonate.

As the triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenyl Sulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethane sulfonate, or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate.

Examples of the quaternary ammonium salts include tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) (P-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate, and the like can be used. .

Diazomethane derivatives such as bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane and the like.

As the imide sulfonate derivative, trifluoromethylsulfonyloxybicyclo [2.2.1] hept-5-ene-dicarboxyimide, succinimide trifluoromethylsulfonate, phthalimide trifluoromethylsulfonate, Hydroxynaphthalimide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimidopropane sulfonate, and the like.

The photosensitive resin composition of the present invention is a photoacid generator having a pKa of the generated acid (component C) of 4 or less and contains an oxime sulfonate compound having at least one oxime sulfonate residue represented by the following formula (c0) desirable. The broken line indicates the bonding position with other chemical structures.

The oxime sulfonate compound having at least one oxime sulfonate moiety represented by the formula (c0) is preferably a compound represented by the following formula (c1).

(Wherein (c1) of, R ⁵ and R ⁶ are each independently, represents a monovalent organic group, R ⁵ and R ⁶ are optionally and connected to form a ring, R ⁷ is alkyl, cycloalkyl, aryl or heteroaryl Lt; / RTI &gt;

In formula (c1), R ⁵ represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, a carbon An acyl group having 2 to 10 atoms, or a cyano group is preferable. The alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic. The alkyl group, alkoxy group or aryl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms .

In the formula (c1), R ⁶ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heterocyclic group having 3 to 10 carbon atoms, , A morpholino group, or a cyano group is preferable. The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic. The heterocyclic group having 3 to 10 carbon atoms may contain an oxygen atom, a sulfur atom, or a nitrogen atom in addition to the carbon atom. The substituent may be a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, An alkoxy group of 1 to 20 carbon atoms. The aryl group, heterocyclic group, or cyclic alkyl group may form a condensed ring with another aliphatic or aromatic ring.

In the formula (c1), R ⁷ is preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be a linear chain. The alkyl group, cycloalkyl group and aryl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a nitro group, a cyano group, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms.

In formula (c1), R ⁵ and R ⁶ may combine with each other to form a 5-membered ring or a 6-membered ring. As the 5-membered or 6-membered ring, an aliphatic carbon ring or a heterocyclic ring can be exemplified. When forming a heterocyclic ring, the hetero atom contained in the heterocyclic ring is preferably an oxygen atom, a sulfur atom, or a nitrogen atom Do. The 5-membered ring or 6-membered ring may have an arbitrary substituent and may be connected to an arbitrary organic group by an unsaturated bond. The 5-membered or 6-membered ring may form a condensed ring with another aliphatic ring, aromatic ring, or heterocyclic ring.

One of the favorable aspects of the oxime sulfonate compound having at least one of the oxime sulfonate moieties represented by formula (c0) is a compound represented by the following formula (c1-1).

(Wherein (c1-1), R ⁷ has a carbon number represents 1-8 alkyl group, a p- Tolu group, a phenyl group, camphor group, a butyl group with methyl group or nonafluoro trifluoroacetic, X is an alkyl group, an alkoxy group, or A halogen atom, t represents an integer of 0 to 3, and when t is 2 or 3, plural Xs may be the same or different)

The alkyl group having 1 to 8 carbon atoms and the nonafluorobutyl group represented by R ⁷ in the formula (c1-1) may be straight chain or branched. The number of carbon atoms of the alkyl group in R ⁷ is preferably 1 to 4, more preferably 1 to 3.

The bonding position of the camphoryl group and the sulfur atom in R ⁷ is not particularly limited, but is preferably in the 10 position. That is, the camphoryl group is preferably a 10-camphoryl group.

The R ⁷ in the formula (c1-1) is preferably a methyl group, an n-propyl group, an n-octyl group, a p-toluyl group, or a camphoryl group, more preferably an n-propyl group, More preferably a di- or camphoryl group, more preferably an n-propyl group or a p-toluyl group.

The alkyl group represented by X is preferably a straight chain or branched chain alkyl group having 1 to 4 carbon atoms.

As the alkoxy group represented by X, a straight chain or branched chain alkoxy group having 1 to 4 carbon atoms is preferable.

The halogen atom represented by X is preferably a chlorine atom or a fluorine atom.

As t, 0 or 1 is preferable.

In the formula (c1-1), t is 1, X is a methyl group, X is a substituted position in the ortho position, R ⁷ is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- A norbornylmethyl group, or a p-toluyl group is particularly preferable.

Specific examples of the oxime sulfonate compound represented by the formula (c1-1) include the following compounds (i), (ii), (iii) and (iv) They may be used singly or in combination of two or more. The compounds (i) to (iv) are commercially available.

It may also be used in combination with other types of photoacid generators.

The oxime sulfonate compound having at least one oxime sulfonate moiety represented by the formula (c0) is preferably a compound represented by the following formula (c3).

(In the formula (c3), R ^B1 represents an alkyl group, an alkoxy group or a halogen atom, and R ^B2 represents an alkyl group or an aryl group)

In formula (c3), R ^B1 is preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. The alkyl group and alkoxy group in R ^B1 may have a substituent, and the alkyl group may be linear, branched, or cyclic. The substituent is preferably a halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group or an alkoxy group having 1 to 4 carbon atoms. R ^B2 is preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. The alkyl group and aryl group in R ^B2 may have a substituent, and the alkyl group may be linear, branched, or cyclic. The substituent is preferably a halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group or an alkoxy group having 1 to 10 carbon atoms.

The R ^B1 in the formula (c3) is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. R ^B2 is preferably an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W, or an anthranyl group optionally substituted with W W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, Halogenated alkoxy groups are preferred.

R ^B2 in the formula (c3) is preferably a methyl group, an ethyl group, a n-propyl group, an n-butyl group, an n-octyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoro- n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and a methyl group, ethyl group, n-propyl group, n-butyl group or p-tolyl group is particularly preferable.

The halogen atom represented by R ^B1 is preferably a fluorine atom, a chlorine atom or a bromine atom.

The alkyl group having 1 to 4 carbon atoms represented by R ^B1 is preferably a methyl group or an ethyl group.

As the alkoxy group having 1 to 4 carbon atoms represented by R ^B1 , a methoxy group or an ethoxy group is preferable.

Of, R ⁵ is wherein the oxime sulfonate compound having at least one of the oxime sulfonate moieties represented by (c0), as a preferred embodiment of the compounds included in the compound represented by the formula (c3), formula (c1), R ⁶ represents a cyano group, and R ⁷ represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a 4-tolyl group.

Hereinafter, particularly preferred examples of the compound represented by formula (c3) among the compounds represented by formula (c1) are shown, but the present invention is not limited thereto.

? - (methylsulfonyloxyimino) benzyl cyanide (R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = methyl group)

(R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = ethyl group)

(R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = n-propyl group)

(R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = n-butyl group), and an α- (n-butylsulfonyloxyimino) benzyl cyanide

(R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = 4-tolyl group)

(R ⁵ = 4-methoxyphenyl, R ⁶ = cyano group, R ⁷ = methyl group)

(R ⁵ = 4-methoxyphenyl, R ⁶ = cyano group, R ⁷ = ethyl group)

(R ⁵ = 4-methoxyphenyl, R ⁶ = cyano group, R ⁷ = n-propyl group)

(R ⁵ = 4-methoxyphenyl, R ⁶ = cyano group, R ⁷ = n-butyl group)

(R ⁵ = 4-methoxyphenyl, R ⁶ = cyano group, R ⁷ = 4-tolyl group)

Examples of the compound having at least one oxime sulfonate residue represented by the formula (c0) include oximesulfosuccinimide represented by the following formula (OS-3), formula (OS-4) It is preferably a compound of the formula (I).

(In the formulas (OS-3) to (OS-5), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, and the plural R ^{2 s} present each independently represent a hydrogen atom, an alkyl group, , X represents O or S, and n is 1 or 2, and R &lt; ^{6 &} gt ;, which is plural in number, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group, And m represents an integer of 0 to 6)

In the above formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group represented by R ¹ may have a substituent.

In the above formulas (OS-3) to (OS-5), the alkyl group represented by R ¹ is preferably an alkyl group having 1 to 30 carbon atoms in total which may have a substituent.

In the above formulas (OS-3) to (OS-5), the aryl group represented by R ¹ is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.

In the above formulas (OS-3) to (OS-5), the heteroaryl group represented by R ¹ is preferably a heteroaryl group having a total of 4 to 30 carbon atoms which may have a substituent, and at least one heteroaryl group For example, a complex aromatic ring and a benzene ring may be condensed.

Examples of the substituent which the alkyl group, aryl group or heteroaryl group represented by R ¹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group have.

In the formulas (OS-3) to (OS-5), R ² is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

Of these formulas (OS-3) to (OS-5), one or two of R ² present in two or more of the compounds are preferably an alkyl group, an aryl group or a halogen atom, and one of R ² is preferably an alkyl group, More preferably an atom, and it is particularly preferable that one is an alkyl group and the remainder is a hydrogen atom.

In the above formulas (OS-3) to (OS-5), the alkyl group or the aryl group represented by R ² may have a substituent.

Examples of the substituent which the alkyl group or aryl group represented by R ² may have include the same group as the substituent that the alkyl group or aryl group in R ¹ may have.

The alkyl group represented by R ² in the formulas (OS-3) to (OS-5) is preferably an alkyl group having 1 to 12 carbon atoms in total which may have a substituent, More preferably an alkyl group.

The alkyl group represented by R ² is preferably a methyl group, ethyl group, n-propyl group, n-butyl group or n-hexyl group, more preferably a methyl group.

In the above formulas (OS-3) to (OS-5), the aryl group represented by R ² is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.

As the aryl group represented by R ² , a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group or p-phenoxyphenyl group is preferable.

Of the above formulas (OS-3) to (OS-5), X represents O or S, and is preferably O.

In the formulas (OS-3) to (OS-5), the ring containing X as reduction is a 5-membered ring or a 6-membered ring.

In the formulas (OS-3) to (OS-5), n represents 1 or 2, and when X is O, n is preferably 1. When X is S, n is 2 desirable.

In the above formulas (OS-3) to (OS-5), the alkyl group and alkyloxy group represented by R ⁶ may have a substituent.

In the above formulas (OS-3) to (OS-5), the alkyl group represented by R ⁶ is preferably an alkyl group having 1 to 30 carbon atoms in total which may have a substituent.

The alkyloxy group represented by R ⁶ is preferably a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group or an ethoxyethyloxy group.

Examples of the aminosulfonyl group for R ⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group and an aminosulfonyl group.

Examples of the alkoxysulfonyl group represented by R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group and a butyloxysulfonyl group.

Examples of the substituent which the alkyl group or alkyloxy group represented by R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group.

In the formulas (OS-3) to (OS-5), m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, Do.

It is particularly preferable that the compound represented by the above formula (OS-3) is a compound represented by the following formula (OS-6), formula (OS-10) or formula (OS- 4) is particularly preferably a compound represented by the following formula (OS-7), and the compound represented by the formula (OS-5) -9) is particularly preferable.

In the formulas (OS-6) to (OS-11), R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ⁷ represents a hydrogen atom or a bromine atom, R ⁸ represents a hydrogen atom, R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R ¹⁰ represents a hydrogen atom or a methyl group, a halogen atom, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, .

The expression (OS-6) ~ R ¹ in (OS-11) is, and R ¹ and agreed in the formula (OS-3) ~ (OS -5), as a preferred aspect.

R ⁷ in the formula (OS-6) represents a hydrogen atom or a bromine atom and is preferably a hydrogen atom.

R ⁸ in the formulas (OS-6) to (OS-11) represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, More preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group, and particularly preferably an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, Do.

R ⁹ in the formulas (OS-8) and (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.

R ¹⁰ in formulas (OS-8) to (OS-11) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

In the oxime sulfonate compound, any of the three-dimensional structures (E, Z) of oxime may be a mixture or a mixture thereof.

Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-3) to (OS-5) include the following exemplified compounds, but the present invention is not limited thereto.

Another favorable embodiment of the oxime sulfonate compound having at least one oxime sulfonate moiety represented by the above formula (c0) includes a compound represented by the following formula (OS-1).

In the formula (OS-1), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, Lt; / RTI &gt; R ² represents an alkyl group or an aryl group.

X is ^{-O-, -S-, -NH-, -NR 5} -, -CH 2 -, -CR 6 H-, or, -CR ⁶ R ⁷ - represents a, R ⁵ ~ R ⁷ is an alkyl group, or Lt; / RTI &gt;

R ²¹ to R ²⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group or an aryl group . Two of R ²¹ to R ²⁴ may be bonded to each other to form a ring.

As R ²¹ to R ²⁴ , a hydrogen atom, a halogen atom, and an alkyl group are preferable, and at least two of R ²¹ to R ²⁴ are bonded to each other to form an aryl group. Among them, the case where all of R ²¹ to R ²⁴ are hydrogen atoms is preferable from the viewpoint of sensitivity.

All of the substituents described above may further have a substituent.

The compound represented by the above formula (OS-1) is more preferably a compound represented by the following formula (OS-2).

The expression (OS-2) of, ^{R 1, R 2, R 21} ~ R 24 are each of the formula and ^{R 1, R 2, R 21} ~ R 24 and agree in (OS-1), preferred examples It is also the same.

Among these, being represented by the formula (OS-1), and the formula (OS-2) R ¹ is a cyano group, or an aryl group sun, and more preferably, the expression (OS-2) in, and the R ¹ A cyano group, a phenyl group or a naphthyl group is most preferable.

In the oxime sulfonate compound, the stereostructure (E, Z, etc.) of oxime or benzothiazole ring may be either or both of them.

Specific examples (Exemplary Compounds b-1 to b-34) of a compound represented by the formula (OS-1) that can be used in the present invention are shown below, but the present invention is not limited thereto. In the specific examples, Me represents a methyl group, Et represents an ethyl group, Bn represents a benzyl group, and Ph represents a phenyl group.

Among these compounds, b-9, b-16, b-31 and b-33 are preferable from the viewpoint of compatibility between sensitivity and stability.

It is preferable that the photosensitive resin composition of the present invention does not contain a 1,2-quinonediazide compound as a photoacid generator (component C) sensitive to an actinic ray. The reason is that the 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but its quantum yield is 1 or less, and the sensitivity is lower than that of the oxime sulfonate compound.

On the other hand, the oxime sulfonate compound acts as a catalyst against deprotection of an acidic group protected by an acid generated in response to an actinic ray, so that an acid generated by the action of one photon contributes to a number of deprotection reactions, It is estimated that the yield is greater than 1, for example, a large value such as 10, and a high sensitivity is obtained as a result of so-called chemical amplification.

The content of the photoacid generator (component C) in the photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight per 100 parts by weight of the total content of the component A and the component B desirable.

<Solvent>

The photosensitive resin composition of the present invention preferably contains a solvent.

The photosensitive resin composition of the present invention is preferably prepared as a solution obtained by dissolving or dispersing the components A, B, C, and optional components of various additives, which will be described later, as essential components in a solvent.

As the solvent to be used in the photosensitive resin composition of the present invention, known solvents can be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene Propylene glycol monoalkyl ether ethers, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Monoalkyl ether acetates, esters, ketones, amides, lactones, and the like.

As the solvent to be used in the photosensitive resin composition of the present invention, for example, diethylene glycol ethyl methyl ether of diethylene glycol dialkyl ethers and / or propylene glycol of propylene glycol monoalkyl ether acetates Monomethyl ether acetate is particularly preferred.

These solvents may be used singly or in combination of two or more kinds.

The solvent which can be used in the present invention is preferably a single solvent or a combination of two solvents, more preferably two solvents, more preferably a diethylene glycol dialkyl ether and a propylene glycol monoalkyl ether acetate It is more preferable to use them in combination.

The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight, more preferably 100 to 2,000 parts by weight, more preferably 150 to 1,500 parts by weight per 100 parts by weight of the total content of component A and component B Is more preferable.

<Other components>

The photosensitive resin composition of the present invention may contain other components.

As the other components, the photosensitive resin composition of the present invention preferably contains a photosensitizer in view of sensitivity, and preferably contains a basic compound from the viewpoint of liquid storage stability. In view of film properties, A crosslinking agent is preferably contained. From the standpoint of substrate adhesion, it is preferable to contain an adhesion improver, and from the viewpoint of coatability, a surfactant is preferably contained.

If necessary, the photosensitive resin composition of the present invention may further contain additives such as a development accelerator, an antioxidant, a plasticizer, a heat radical generator, a thermal acid generator, an acid propagation agent, an ultraviolet absorber, a thickener and an organic or inorganic precipitation inhibitor , A known additive may be added.

Hereinafter, other components that may be contained in the photosensitive resin composition of the present invention will be described.

<Optical sensitizer>

The photosensitive resin composition of the present invention preferably contains a photosensitizer.

By containing a photosensitizer, it is effective for improving the exposure sensitivity, and the exposure light source is particularly effective in the case of g and h line mixed lines.

As the photosensitizer, anthracene derivatives, acridone derivatives, thioxanthone derivatives, coumarin derivatives, basestyryl derivatives, and distyrylbenzene derivatives are preferable.

Examples of the anthracene derivative include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, , 9,10-dibromoanthracene, 2-ethyl anthracene, and 9,10-dimethoxy anthracene are preferable.

As the acridone derivative, acridone, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone and N-ethyl-2-methoxyacridone are preferable.

As the thioxanthone derivative, thioxanthone, diethyl thioxanthone, 1-chloro-4-propanedioxanthone, and 2-chlorothioxanthone are preferable.

As coumarin derivatives, coumarin-1, coumarin-6H, coumarin-110 and coumarin-102 are preferable.

Examples of the base styryl derivative include 2- (4-dimethylaminostyryl) benzoxazole, 2- (4-dimethylaminostyryl) benzothiazole and 2- (4-dimethylaminostyryl) naphthothiazole. have.

Examples of the distyrylbenzene derivative include distyrylbenzene, di (4-methoxystyryl) benzene and di (3,4,5-trimethoxystyryl) benzene.

Of these, anthracene derivatives are preferable, and 9,10-dialkoxyanthracene (having 1 to 6 carbon atoms in the alkoxy group) is more preferable.

Specific examples of the photosensitizer include the following. In the following, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

The content of the photosensitizer in the photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total content of Component A and Component B. If it is within the above-mentioned numerical value range, desired sensitivity is easily obtained and is preferable.

&Lt; Basic compound >

The photosensitive resin composition of the present invention preferably contains a basic compound from the viewpoint of liquid storage stability.

The basic compound can be arbitrarily selected from those used in chemical amplification resistors. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

Examples of the aliphatic amine include aliphatic amines such as trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di- , Triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.

Examples of heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, Benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8- Pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N '- [2- (4-morpholinyl ) Ethyl] thiourea, 1,5-diazabicyclo [4.3.0] -5-nonene, and 1,8-diazabicyclo [5.3.0] -7-undecene.

Examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide and tetra-n-hexylammonium hydroxide. have.

Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate and tetra-n-butylammonium benzoate.

The basic compounds which can be used in the present invention may be used singly or in combination of two or more kinds. However, two or more kinds of basic compounds are preferably used, more preferably two kinds of basic compounds, It is more preferable to use them in combination.

The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by weight, more preferably 0.002 to 0.5 part by weight based on 100 parts by weight of the total content of the component A and the component B.

<Cross-linking agent>

The photosensitive resin composition of the present invention preferably contains a crosslinking agent, if necessary. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made into a stronger film.

As the crosslinking agent, for example, a block isocyanate crosslinking agent, a compound having two or more epoxy groups or oxetanyl groups in the molecule, an alkoxymethyl group-containing crosslinking agent such as an alkoxymethylated melamine compound, or a crosslinking agent containing at least one ethylenically unsaturated double bond And the like can be added.

Among them, a block isocyanate-based cross-linking agent is particularly preferable from the viewpoints of resist sensitivity and storage stability. In addition, an alkoxymethyl group-containing crosslinking agent can also be used suitably, among which methylol melamine compounds are more preferable.

The amount of the crosslinking agent to be added to the photosensitive resin composition of the present invention is preferably 0.05 to 50 parts by weight, more preferably 0.2 to 40 parts by weight, more preferably 0.5 to 30 parts by weight, relative to the total solid content of the photosensitive resin composition Do. By adding in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained.

- Block isocyanate cross-linking agent -

The block isocyanate cross-linking agent is not particularly limited as long as it is a compound having a block isocyanate group (block isocyanate compound), but from the viewpoint of curability, it is preferably a compound having two or more block isocyanate groups in one molecule.

The block isocyanate group in the present invention is a group capable of generating an isocyanate group by heat, and for example, a group in which an isocyanate group is protected by reacting a block agent with an isocyanate group can be preferably exemplified. It is preferable that the block isocyanate group is a group capable of producing an isocyanate group by heat at 90 ° C to 250 ° C.

The skeleton of the block isocyanate-based crosslinking agent is not particularly limited, and a skeleton of a hexamethylene diisocyanate (HDI) skeleton, an isophorone diisocyanate (IPDI) skeleton, and a skeleton of a prepolymer derived from HDI or IPDI It can be used for personal use.

The blocking agent of the isocyanate group in the block isocyanate group is not particularly limited and an active hydrogen compound such as an active methylene compound such as a diester compound, an oxime compound, a lactam compound, or an amine compound can be preferably used. Of these, active methylene compounds are particularly preferable from the viewpoint of reactivity.

Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate.

Examples of the oxime compounds include cyclohexanone oxime, benzophenone oxime, acetoxime, and the like.

Examples of the lactam compound include ε-caprolactam, γ-butyrolactam, and the like.

Examples of the amine compound include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.

The active hydrogen compound reacts with an isocyanate group to form a block isocyanate group as shown in the following formula.

R-NCO + H-R '? R-NH-C (= O)

(Wherein H - R 'represents an active hydrogen compound, H in H - R' represents an active hydrogen atom, R represents a part other than the isocyanate group in the isocyanate compound, and R ' Represents a portion other than the active hydrogen atom in the hydrogen compound)

These block isocyanate-based cross-linking agents are available as commercial products and include, for example, dyrenate MF-K60X, MF-K60B, MF-B60X, 17B-60P, TPA-B80E, E402-B80B, SBN-70D and K6000 (Manufactured by Asahi Chemical Industry Co., Ltd.), Desmodule BL3272, BL3575 / 1 (manufactured by Sumika Bayer Urethane Co., Ltd.) and Urethane PUR-1804 (manufactured by DIC Corporation). Of these, DURANATE MF-K60X, MF-K60B, 17B-60P, SBN-70D and K6000 are particularly preferable.

The amount of the block isocyanate crosslinking agent to be added to the photosensitive resin composition of the present invention is preferably from 0.1 to 30 parts by weight, more preferably from 0.2 to 20 parts by weight based on 100 parts by weight of the total amount of the component A and the component B, More preferably 0.5 to 15 parts by weight.

- crosslinking agent containing an alkoxymethyl group -

As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril and alkoxymethylated urea are preferable. These are obtained by converting the methylol groups of methylol melamine, methylol benzoguanamine, methylol glycoluryl, or methylol groups into alkoxymethyl groups, respectively. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of the amount of generated outgas, a methoxymethyl group .

Of these alkoxymethyl group-containing crosslinking agents, alkoxymethylated melamine compounds are more preferable crosslinking agents, and melamine compounds in which the nitrogen atom of the amino group is substituted with a methoxymethyl group are particularly preferable.

These alkoxymethyl group-containing crosslinking agents are commercially available, for example, from Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123 , 1170, 1174, UFR65, 300 (manufactured by Mitsui Cyanamid), NIKARAK MX-750, -032, -706, -708, -40, -31, -270, -280, -290 , NIKARAK MS-11, NIKARAK MW-30HM, -100 LM, -390 (manufactured by SANWA CHEMICAL Co., Ltd.), and the like.

When an alkoxymethyl group-containing crosslinking agent is used in the photosensitive resin composition of the present invention, the addition amount of the alkoxymethyl group-containing crosslinking agent is preferably 0.05 to 30 parts by weight, more preferably 0.2 to 10 parts by weight per 100 parts by weight of the total content of the component A and the component B By weight is more preferable. When added in this range, favorable alkali solubility at the time of development and excellent solvent resistance of the film after curing can be obtained.

- a compound having two or more epoxy groups or oxetanyl groups in the molecule -

Specific examples of the compound having two or more epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin and aliphatic epoxy resin.

These are available as commercial products. Examples of the bisphenol A epoxy resin include epoxy resins such as JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (Manufactured by DIC Corporation), and the bisphenol F type epoxy resins include JER806, JER807, JER4004, JER4005, JER4007 and JER4010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 ), LCE-21, RE-602S (manufactured by Nihon Kayaku Co., Ltd.), and phenol novolak type epoxy resins such as JER152, JER154, JER157S70, JER157S65 EPICLON N-760, EPICLON N-770, EPICLON N-775 (manufactured by DIC Corporation), and EPICLON N-660 and EPICLON N-665 EPICLON N-670, EPICLON N-670, EPICLON N-670, EPICLON N-680, EPICLON N-690, EPICLON N-695 (manufactured by DIC Corporation), EOCN-1020 (manufactured by Nihon Kayaku Co., Ltd.) As the aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA), Celllock 2021P, Celllock 2081, Celllock 2083, Celllock 2085, EHPE 3150, EPOLEAD PB 3600, , Daicel Kagaku Kogyo Co., Ltd.) and the like. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD- -501, and EPPN-502 (manufactured by ADEKA Co., Ltd.).

These may be used alone or in combination of two or more.

Among them, an epoxy resin is preferable, and a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a phenol novolak type epoxy resin are more preferable, and a bisphenol A type epoxy resin is particularly preferable have.

As specific examples of the compound having two or more oxetanyl groups in the molecule, Aromoxetane OXT-121, OXT-221, OX-SQ and PNOX (all manufactured by Doago Kosai Co., Ltd.) can be used.

The oxetanyl group-containing compound is preferably used alone or in combination with a compound containing an epoxy group.

The amount of the compound having two or more epoxy groups or oxetanyl groups in the molecule to be added to the photosensitive resin composition of the present invention is preferably 0.5 to 50 parts by weight and more preferably 1 to 100 parts by weight based on 100 parts by weight of the total content of Component A and Component B. [ More preferably 30 parts by weight.

- a compound having at least one ethylenically unsaturated double bond -

As the compound having at least one ethylenic unsaturated double bond, a (meth) acrylate compound such as monofunctional (meth) acrylate, bifunctional (meth) acrylate or trifunctional or higher functional (meth) have.

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl And 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate.

Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol (meth) acrylate, polypropylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, and bisphenoxyethanol fluorene diacrylate.

Examples of trifunctional or higher (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

These compounds having at least one ethylenic unsaturated double bond may be used singly or in combination of two or more.

The proportion of the compound having at least one ethylenically unsaturated double bond in the photosensitive resin composition of the present invention is preferably 50 parts by weight or less based on 100 parts by weight of the total content of the component A and the component B, Or less. When a compound having at least one ethylenically unsaturated double bond is added, it is preferable to add a heat radical generator described later.

&Lt; Adhesion improving agent &

The photosensitive resin composition of the present invention preferably contains an adhesion improver from the viewpoint of substrate adhesion.

The adhesion improver that can be used in the photosensitive resin composition of the present invention may be an inorganic compound such as a silicon compound such as silicon, silicon oxide, or silicon nitride, a silicon compound such as molybdenum, titanium, indium tin oxide, gold, It is a compound that improves the adhesion between the metal and the insulating film. Specific examples thereof include silane coupling agents and thiol compounds. The silane coupling agent used as the adhesion improver for use in the present invention is not specifically limited and any known silane coupling agent may be used for the purpose of modifying the interface. Among them, a silane coupling agent can be preferably exemplified.

Preferable silane coupling agents include, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? -Methacryloxypropylalkyldialkoxysilane,? -Chloropropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyl tri Alkoxysilane, and vinyltrialkoxysilane.

Of these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable, and? -Glycidoxypropyltrialkoxysilane is more preferable.

These are available as commercial products. Compounds containing an epoxy group such as KBM-303, -402, -403, KBE-402 and -403, methacrylic group-containing compounds such as KBM-502, -503, KBE- 603, -903, -573, -575, KBE-603, and -9103 (the above compounds are manufactured by Shin-Etsu Chemical Co., Ltd.).

The following compounds may also be preferably used.

In the formula, Ph represents a phenyl group.

These may be used alone or in combination of two or more.

The content of the adhesion improver in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, per 100 parts by weight of the total content of Component A and Component B.

<Surfactant>

The photosensitive resin composition of the present invention preferably contains a surfactant from the viewpoint of coatability.

As the surfactant, any of anionic, cationic, nonionic or amphoteric surfactants can be used, but preferred surfactants are nonionic surfactants.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine series, and silicone surfactants.

It is more preferable that the photosensitive resin composition of the present invention contains a fluorine-based surfactant and / or a silicon-based surfactant as a surfactant.

As the fluorine-based surfactant and the silicon-based surfactant, there can be mentioned, for example, Japanese Patent Application Laid-Open Nos. 62-36663, 61-226746, 61-226745, 62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2001-330953, And a commercially available surfactant may be used.

(Commercially available from Shin-Akita Kasei Co., Ltd.), Fluorad FC430, 431 (manufactured by Sumitomo 3M Ltd.), Megaface (available from Sumitomo Chemical Co., Ltd.) F171, F173, F176, F189, F554 and R08 (manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105 and 106 (manufactured by Asahi Glass Co., Fluorine surfactants such as PolyFox series (manufactured by OMNOVA), and silicone surfactants. The polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

The surfactant preferably has a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography when the surfactant contains the constituent unit A and the constituent unit B represented by the following formula (1) and tetrahydrofuran (THF) (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferable example.

(Wherein R ¹ and R ³ are each independently a hydrogen atom or a methyl group, R ² is a straight chain alkylene group having 1 to 4 carbon atoms and R ⁴ is a hydrogen atom or a C1- P represents an alkylene group having 3 to 6 carbon atoms, p and q represent weight percentages representing polymerization ratios, p represents a value of 10 to 80 wt%, q represents 20 wt% Or more and 90% or less by weight, r is an integer of 1 or more and 18 or less, and n is an integer of 1 or more and 10 or less)

It is preferable that L is a branched alkylene group represented by the following formula (2). R ⁵ in the formula (2) represents an alkyl group having 1 to 4 carbon atoms and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to a surface to be coated, and an alkyl group having 2 or 3 carbon atoms More preferable.

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

These surfactants may be used singly or in combination of two or more.

The amount of the surfactant added to the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, more preferably 0.01 to 10 parts by weight, and most preferably 0.01 to 1 part by weight, per 100 parts by weight of the total content of Component A and Component B. More preferably by weight.

&Lt; Development accelerator &

The photosensitive resin composition of the present invention preferably contains a development accelerator.

As the development accelerator, any compound having a phenomenon of promoting development can be used, but it is preferably a compound having at least one kind of group selected from the group of a carboxyl group, a phenolic hydroxyl group and an alkyleneoxy group, and a carboxyl group or a phenolic hydroxyl group Is more preferable, and a compound having a phenolic hydroxyl group is most preferable.

The molecular weight of the development promoter is preferably 100 to 2,000, more preferably 150 to 1,500, and particularly preferably 150 to 1,000.

As examples of the development accelerator, those having an alkyleneoxy group include polyethylene glycol, monomethyl ether of polyethylene glycol, dimethyl ether of polyethylene glycol, polyethylene glycol glyceryl ester, polypropylene glycol glyceryl ester, polypropylene glycol diglyceryl ester , Polybutylene glycol, polyethylene glycol-bisphenol A ether, polypropylene glycol-bisphenol A ether, alkyl ether of polyoxyethylene, alkyl ester of polyoxyethylene, and compounds described in Japanese Patent Application Laid-Open No. 9-222724 .

Examples of compounds having a carboxyl group include compounds described in Japanese Patent Application Laid-Open Nos. 2000-66406, 9-6001, 10-20501, 11-338150, and the like.

Examples of those having a phenolic hydroxyl group include those disclosed in JP-A Nos. 2005-346024, 10-133366, 9-194415, 9-222724, 11-171810 Compounds described in JP-A-2007-121766, JP-A-9-297396, JP-A-2003-43679 and the like can be enumerated. Among them, phenol compounds having 2 to 10 benzene ring numbers are preferred, and phenol compounds having 2 to 5 benzene ring numbers are more preferable. Particularly preferred examples include phenolic compounds disclosed as dissolution accelerators in JP-A-10-133366.

The development accelerator may be used alone or in combination of two or more.

The addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight, based on 100 parts by weight of the total content of the component A and the component B from the viewpoints of sensitivity and residual film ratio More preferably 0.5 to 10 parts by weight.

<Antioxidant>

The photosensitive resin composition of the present invention may contain an antioxidant.

As the antioxidant, a known antioxidant may be contained. By adding an antioxidant, coloring of the cured film can be prevented, or film thickness reduction due to decomposition can be reduced, and furthermore, there is an advantage that the heat resistance and transparency are excellent.

Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur-based antioxidants, phenol-based antioxidants, ascorbic acids, zinc sulfate, sugars, nitrite, sulfite, thiosulfate, hydroxyl Amine derivatives and the like. Among them, a phenol-based antioxidant is particularly preferable from the viewpoint of coloring of the cured film and reduction of the film thickness. These may be used alone or in combination of two or more.

Examples of commercially available products of phenolic antioxidants include adekastab AO-15, adekastab AO-18, adekastab AO-20, adekastab AO-23, adekastab AO- 30, Adekastab AO-37, Adekastab AO-40, Adekastab AO-50, Adekastab AO-51, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-330, Adekastab AO-412S, Adekastab AO-503, Adekastab A-611, Adekastab A- Adekastab PEP-8, Adekastab PEP-8W, Adekastab PEP-24G, Adekastab PEP-36, Adekastab PEP- PEP-36Z, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adeka Stab 135A, Adekastab 3010, Adekastab TPP, Adekastab CDA-1, Adekastab CDA-6, Adekastab ZS-27, Adekastab ZS-90, Adekastab ZS-91 (manufactured by ADEKA Corporation), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irgalox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irganox 168, Irgas mode 1035, Irganox 1098, Irganox 1398, Ltd.), and the like. Above all, Adekastab AO-60, Adekastab AO-80, Irganox 1726, Irganox 1035, Irganox 1098 can be used as a family.

The content of the antioxidant is preferably 0.1 to 6% by weight, more preferably 0.2 to 5% by weight, and particularly preferably 0.5 to 4% by weight based on the total solid content of the photosensitive resin composition. When the content is in this range, sufficient transparency of the formed film can be obtained and sensitivity at the time of pattern formation can be improved.

As the additives other than the antioxidants, various ultraviolet absorbers, metal deactivators, and the like described in &quot; New developments of polymer additives (Nikken Chemical Co., Ltd.) &quot; may be added to the photosensitive resin composition of the present invention.

<Plasticizer>

The photosensitive resin composition of the present invention may contain a plasticizer.

Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerine phthalate, dibutyl tartrate, dioctyl adipate, triacetyl glycerin and the like.

The content of the plasticizer in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the total content of Component A and Component B.

&Lt; Heat radical generator >

The photosensitive resin composition of the present invention may contain a thermal radical generator and, when containing an ethylenically unsaturated compound such as a compound having at least one ethylenically unsaturated double bond as described above, may contain a thermal radical generator desirable.

As the thermal radical generator in the present invention, a known thermal radical generator may be used.

The thermal radical generator is a compound which generates radicals by the energy of heat and initiates or promotes the polymerization reaction of the polymerizable compound. By adding the heat radical generator, the cured film obtained becomes stronger, and heat resistance and solvent resistance may be improved in some cases.

Preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbimidazole compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, A compound having a bond, an azo-based compound, and a non-benzyl compound.

As the thermal radical generator, one type may be used alone, or two or more types may be used in combination.

The content of the thermal radical generator in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the total content of component A and component B, More preferably 0.5 to 10 parts by weight.

<Thermal acid generator>

In the present invention, a thermal acid generator may be used in order to improve physical properties of the film in low-temperature curing.

The thermal acid generator which can be used in the present invention is a compound which generates acid by heat and is a compound having a thermal decomposition point preferably in a range of 130 ° C to 250 ° C, more preferably 150 ° C to 220 ° C, (Low nucleophilic) acid such as sulfonic acid, carboxylic acid, disulfonylimide and the like.

As the acid generated by the thermal acid generator, a disulfonylimide substituted with an electron-withdrawing group such as a sulfonic acid or an alkyl or arylcarboxylic acid substituted with an electron-withdrawing group Do. Examples of the electron-withdrawing group include a halogen atom such as a fluorine atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

In the present invention, it is also preferable to use a sulfonic acid ester which generates an acid by heat without generating an acid substantially by irradiation with exposure light.

The fact that substantially no acid is generated by the irradiation of the exposure light can be determined by measuring the IR spectrum before or after exposure of the compound or by measuring the NMR spectrum without any change in the spectrum.

The molecular weight of the sulfonic acid ester is preferably from 230 to 1,000, more preferably from 230 to 800.

The sulfonic acid ester which can be used in the present invention may be a commercially available one or a synthesized one synthesized by a known method. The sulfonic acid ester can be synthesized, for example, by reacting a sulfonyl chloride or a sulfonic acid anhydride with a corresponding polyhydric alcohol under basic conditions.

The content of the thermal acid generator in the photosensitive resin composition is preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the total content of the component A and the component B. [

<Acid-proliferating agent>

In the photosensitive resin composition of the present invention, an acid propagating agent may be used for the purpose of improving the sensitivity.

The acid-proliferating agent usable in the present invention is a compound capable of generating an acid by further acid catalysis reaction to raise the acid concentration in the reaction system, and is a compound stably present in the absence of acid. Such a compound accelerates the reaction in accordance with the progress of the reaction because one or more acids are elongated in one reaction. However, since the resulting acid itself undergoes self-decomposition, It is preferable that the integer pKa is 3 or less, particularly 2 or less.

Specific examples of the acid proliferating agent include those described in paragraphs 0203 to 0223 of JP-A No. 10-1508, paragraphs 0016 to 0055 of JP-A No. 10-282642, and JP-A No. 9-512498, page 39, To page 47, the second line.

Examples of the acidic proliferative agent that can be used in the present invention include acids decomposed by acids generated from an acid generator and decomposed with pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid and phenylphosphonic acid Is 3 or less.

The content of the acid proliferating agent in the photosensitive resin composition is preferably from 10 to 1,000 parts by weight based on 100 parts by weight of the photoacid generator from the viewpoint of dissolution contrast between the exposed portion and the unexposed portion and is preferably from 20 to 500 parts by weight More preferable.

(Method of forming a cured film)

Next, a method of forming the cured film of the present invention will be described.

The method for forming a cured film of the present invention preferably includes the following steps (1) to (4).

(1) A coating process for applying the positive photosensitive resin composition of the present invention onto a substrate

(2) an exposure step of exposing the applied photosensitive resin composition by an actinic ray,

(3) a developing step of developing the exposed photosensitive resin composition with an aqueous developing solution, and

(4) a post-baking step of thermally curing the developed photosensitive resin composition

Each step will be described below in order.

(1), the photosensitive resin composition of the present invention is applied onto a substrate to form a wet film containing a solvent.

When the positive photosensitive resin composition of the present invention contains a solvent, the method of forming a cured film of the present invention is preferably a method of forming a cured film from a coated photosensitive resin composition to a solvent (1) And a solvent removing step of removing the solvent.

In the solvent removing step, the solvent is removed from the coated film by reduced pressure (vacuum) and / or heating to form a dry coating film on the substrate.

In the exposure step of (2), the obtained coating film is irradiated with an actinic ray having a wavelength of 300 nm or more and 450 nm or less. In this step, the photoacid generator decomposes and generates acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the component A is decomposed to generate an acid group.

Post-exposure heat treatment: Post Exposure Bake (hereinafter, also referred to as &quot; PEB &quot;) can be performed, if necessary, in order to accelerate the above hydrolysis reaction in the region where the acid catalyst is produced. By PEB, the generation of carboxyl groups from the acid decomposable group can be promoted.

The acid decomposable group in the component A in the present invention is low in the activation energy of acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate an acid group. Thereby forming a positive image.

By performing PEB at a relatively low temperature, the hydrolysis of the acid decomposable group can be promoted without causing a crosslinking reaction. The temperature at which PEB is carried out is preferably 30 占 폚 to 130 占 폚, more preferably 40 占 폚 to 110 占 폚, and particularly preferably 50 占 폚 to 80 占 폚.

(3), the resin having an advantageous acid group is developed using an alkaline developer. A positive image is formed by removing an exposed region formed of a composition containing a resin having an acid group which is likely to dissolve in an alkaline developer.

The cured film can be formed by thermally decomposing an acid-decomposable group in the component A to generate an acid group by crosslinking with the crosslinkable group by heating the obtained positive image in the post-baking step of the step (4). This heating is preferably performed at a high temperature of 150 ° C or higher, more preferably 180 ° C to 250 ° C, and particularly preferably 200 ° C to 250 ° C. The heating time can be appropriately set depending on the heating temperature and the like, but is preferably within a range of 10 to 90 minutes.

When a step of irradiating the entire surface of the development pattern with an actinic ray, preferably ultraviolet light, before the post-baking step is added, the cross-linking reaction can be promoted by the acid generated by the actinic light irradiation.

Next, a method for forming a cured film using the photosensitive resin composition of the present invention will be described in detail.

&Lt; Preparation method of photosensitive resin composition >

A photosensitive resin composition is prepared by mixing a specific resin component and an essential component of a photo-acid generator, if necessary, with a solvent in a predetermined ratio and optionally by stirring and dissolving. For example, a photosensitive resin composition may be prepared by preparing a solution in which a specific resin or photoacid generator is dissolved in each solvent in advance, and mixing them in a predetermined ratio. The solution of the photosensitive resin composition prepared as described above may be used after being filtered using a filter having a pore size of 0.2 탆 or the like.

<Coating Process and Solvent Removal Process>

The desired dry film can be formed by applying the resin composition to a predetermined substrate and removing the solvent by reduced pressure and / or heating (prebaking). Examples of the above substrate include a polarizing plate and a glass plate provided with a black matrix layer and a color filter layer as necessary and provided with a transparent conductive circuit layer in the production of a liquid crystal display element. The coating method on the substrate is not particularly limited, and for example, a slit coating method, a spraying method, a roll coating method, and a spin coating method can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Here, a large substrate refers to a substrate having a size of 1 m or more on each side.

The heating condition in the solvent removal step is a range in which the acid-decomposable group in the component A in the unexposed portion decomposes and the component A is not soluble in an alkali developing solution. The heating condition varies depending on the kind of each component and the blending ratio, , It is about 80 to 130 DEG C for about 30 to 120 seconds.

&Lt; Exposure step and development step (pattern formation method) >

In the exposure step, the substrate provided with a coating film is irradiated with an actinic ray through a mask having a predetermined pattern. After the exposure process, the substrate is subjected to heat treatment (PEB) as required, and in the development process, an alkaline developer is used and the exposed area is removed to form an image pattern.

(436 nm), i-line (365 nm), h-line (405 nm), and the like can be used for the exposure by the active light beam. Nm) or the like having a wavelength of 300 nm or more and 450 nm or less can be preferably used. If necessary, irradiation light can be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.

A basic compound is used for the developing solution used in the developing process. Examples of the basic compound include alkali metal hydroxide such as lithium hydroxide, sodium hydroxide and potassium hydroxide; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline hydroxide; An aqueous solution of sodium silicate, sodium metasilicate or the like can be used. An aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the aqueous alkaline solution may be used as a developer.

The pH of the developing solution is preferably 10.0 to 14.0.

The developing time is preferably 30 to 180 seconds, and the developing method may be any of a liquid method, a dipping method, and the like. After development, a desired pattern can be formed by conducting water washing for 30 to 90 seconds.

&Lt; Post baking step (crosslinking step) >

For a predetermined time at a predetermined temperature, for example, 180 to 250 DEG C for a predetermined time, for example, 5 DEG C on a hot plate, using a heating apparatus such as a hot plate or an oven with respect to a pattern corresponding to the unexposed region obtained by development For 60 minutes in an oven and for 30 to 90 minutes in an oven to decompose the acid decomposable group in the component A to generate an acid group and react with the crosslinkable group in the component A and the component B to perform crosslinking , Heat resistance, hardness, and the like can be formed. The heat treatment may be carried out in a nitrogen atmosphere to improve transparency.

Prior to the heat treatment, the substrate on which the pattern is formed is re-exposed by an actinic ray, and then post-baking (re-exposure / post-baking) is performed to generate an acid present in the unexposed portion to accelerate the cross- As a catalyst.

That is, the method for forming a cured film of the present invention preferably includes a re-exposure step for re-exposure by an actinic ray between the developing step and the post-baking step.

The exposure in the re-exposure step may be carried out by the same method as in the above-mentioned exposure step, but in the re-exposure step, it is preferable to perform the whole exposure on the side of the substrate where the film is formed by the photosensitive resin composition of the present invention. A preferable exposure amount of the re-exposure step is 100 to 1,000 mJ / cm &lt; 2 &gt;.

With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent transparency can be obtained even when the insulating resin is baked at a high temperature. The interlayer insulating film formed using the photosensitive resin composition of the present invention is useful for an organic EL display device and a liquid crystal display device because it has high transparency and excellent physical properties of a cured film.

The organic EL display device and the liquid crystal display device of the present invention are not particularly limited except that they have a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention and may be various known organic EL displays Device or a liquid crystal display device.

Further, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above-mentioned applications, and can be used for various applications. For example, in addition to a planarizing film and an interlayer insulating film, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state image pickup device, and the like can be used.

1 is a conceptual diagram showing an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarization film 4.

A bottom gate type TFT 1 is formed on a glass substrate 6 and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A wiring 2 (height 1.0 mu m) connected to the TFT 1 is formed in the insulating film 3 by forming a contact hole in which the contact hole is omitted in this example, (Not shown). The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or in a subsequent step to the TFT 1. [

The planarization layer 4 is formed on the insulating film 3 in a state of embedding (embedding) irregularities by the wirings 2 in order to planarize the irregularities formed by the formation of the wirings 2.

On the planarizing film 4, a bottom-emission organic EL element is formed. That is, a first electrode 5 made of ITO is formed on the planarizing film 4 by being connected to the wiring 2 via the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.

The insulating film 8 is formed so as to cover the periphery of the first electrode 5. By providing the insulating film 8, the first electrode 5 and the second electrode It is possible to prevent a short circuit between the electrodes.

Although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially evaporated through a desired pattern mask. Then, a second electrode made of Al is formed on the entire upper surface of the substrate, It is possible to obtain an active matrix type organic EL display device in which a glass plate and an ultraviolet curable epoxy resin are used for sealing to each other and the TFTs 1 for driving the organic EL elements are connected to each other.

2 is a conceptual cross-sectional view showing an example of the liquid crystal display device 10 of the active matrix type. This color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on its back surface and the liquid crystal panel is disposed between two glass substrates 14 and 15 to which a polarizing film is pasted And elements of the TFT 16 corresponding to all the pixels are disposed. In each element formed on the glass substrate, an ITO transparent electrode 19 for forming a pixel electrode is wired through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a layer of the liquid crystal 20 and a black matrix are arranged is provided.

[Example]

Next, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited by these examples. Unless otherwise noted, "parts" and "%" are by weight.

In Table 1 to Table 4, "-" indicates no content.

&Lt; Synthesis Example 1 &

A cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) 200 parts by weight of ether were added. Subsequently, 65.1 parts by weight of 1-ethoxyethyl methacrylate, 54.0 parts by weight of 3-ethyl-3-oxetanylmethyl methacrylate, 8.4 parts by weight of methacrylic acid, 25.5 parts by weight of hydroxyethyl methacrylate, -Methylstyrene dimer (manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was purged with nitrogen, and stirring was started slowly. The temperature of the solution was raised to 70 캜 and maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer (A-1). The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A-1) was 11,000.

Table 1 shows the composition ratios (molar equivalents) of the synthesized copolymers.

&Lt; Synthesis Examples 2 to 10 &

(A-2) to (A-8), (a-1) and (a-2) shown in Table 1 were synthesized in the same manner as in Synthesis Example 1 except that the monomers used and the amounts thereof were changed. did. The composition ratios (molar equivalents) and weight average molecular weights (Mw) of the respective synthesized copolymers are shown in Table 1.

[Table 1]

&Lt; Synthesis Example 11 &

(35.7 g, manufactured by Tohoku Kagaku Kogyo Co., Ltd.) as a solvent was placed in a three-necked flask, and the temperature was raised to 90 캜 under a nitrogen atmosphere. To the solution was added styrene (13.32 g), N-butoxymethylacrylamide (20.11 g), methacrylic acid (7.86 g), methyl methacrylate (1.83 g), dimethyl 2,2'-azobis (2-methylpropionate) (V-601, 3.47 g, manufactured by Wako Pure Chemical Industries, Ltd., 8 mol% based on the monomer) was dissolved and dissolved dropwise over 2 hours. After completion of dropwise addition, stirring was continued for 2 hours. V-601 (1.84 g, 2 mol% based on the monomer) was further added to the solution, and the reaction was terminated by further stirring for 2 hours. Thus, Copolymer B-1 was obtained. The weight average molecular weight was 19,000.

The composition ratios (molar equivalents) of the synthesized copolymers are shown in Table 2.

&Lt; Synthesis Examples 12 to 24 &

(B-2) to (B-12), (b-1) and (b-2) shown in Table 2 were synthesized in the same manner as in Synthesis Example 11 except that the monomers used and the amounts thereof were changed. did. The composition ratios (molar equivalents) and weight average molecular weights (Mw) of the respective synthesized copolymers are shown in Table 2.

[Table 2]

The abbreviations in Tables 1 and 2 are as follows.

MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

MATHF: tetrahydrofuran-2-yl methacrylate (synthetic)

OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.)

GMA: glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

NBMA: N-n-butoxymethyl acrylamide (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

VBGE: p-vinylbenzyl glycidyl ether (synthesized according to the method described in paragraphs 0037 to 0039 of JP-A-9-227540)

MAA: methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)

HEMA: 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

St: Styrene (manufactured by Wako Pure Chemical Industries, Ltd.)

MMA: methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

DCPM: methacrylic acid (tricyclo [5.2.1.0 ^2,6 ] decan-8-yl) (FA-511A, manufactured by Hitachi Chemical Co., Ltd.)

THFFMA: tetrahydrofurfuryl methacrylate (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.)

(Examples 1 to 37 and Comparative Examples 1 to 7)

(Solid content weight) shown in Tables 3 and 4 was added to a mixed solvent of diethylene glycol methyl ethyl ether: propylene glycol monomethyl ether acetate = 1: 1 (weight ratio) so that the solid content concentration became 20 wt% And then filtered through a membrane filter having a diameter of 0.2 탆 to prepare photosensitive resin compositions of Examples 1 to 37 and Comparative Examples 1 to 7, respectively.

[Table 3]

[Table 4]

Details of the abbreviations indicating the compounds used in Examples 1 to 37 and Comparative Examples 1 to 7 are as follows.

C-1: Compound of the following structure (synthesized product)

C-2: Compound of the following structure (synthesized product)

C-3: Compound of the following structure (synthesized product)

C-4: CGI-1397 (BASF)

C-5: Compound of the following structure (synthesized according to the method described in paragraph 0108 of Japanese Patent Specification No. 2002-528451)

C-6: PAI-1001 (manufactured by Midori Kagaku Co., Ltd.)

C-7: 1,2-naphthoquinonediazide-5-sulfonic acid ester of 2,3,4-trihydroxybenzophenone (pKa of the generated acid = 4.5, Synthesis, in paragraph 0027 of Patent No. 2753912 Synthesized according to the described method)

&Lt; Synthesis Example 1: Synthesis of MATHF >

50.33 g (0.585 mol) of methacrylic acid and 0.27 g (0.2 mol%) of camphorsulfonic acid were mixed in a three-necked flask and cooled to 15 캜. 41.00 g (0.585 mol) of 2,3-dihydrofuran was added dropwise to the solution. A saturated aqueous sodium bicarbonate solution (500 mL) was added to the reaction solution, extracted with ethyl acetate (500 mL), and dried over magnesium sulfate. The insoluble material was filtered and concentrated under reduced pressure to a temperature of 40 ° C or lower. The colorless oil phase of the residue was distilled under reduced pressure to obtain 73.02 g of MATHF having a boiling point (bp.) Of 54 to 56 ° C / 3.5 mmHg.

<Synthesis of C-1>

Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 캜 for reaction for 2 hours. 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution under ice cooling, and ethyl acetate (50 mL) was added to separate the layers. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 占 폚 for 1 hour. 2N HCI aqueous solution (60 mL) was added thereto to separate the liquid. The organic layer was concentrated, and crystals were dissolved in diisopropyl ether Filtered, and dried to obtain a ketone compound (6.5 g).

Acetic acid (7.3 g) and a 50 wt% hydroxylamine aqueous solution (8.0 g) were added to the suspension of the resulting ketone compound (3.0 g) and methanol (18 mL), and the mixture was heated under reflux for 10 hours. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).

The resulting oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, the temperature was raised to 25 캜, . Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered and then slurry was reslurried with methanol (20 mL), followed by filtration and drying to obtain C-1 (2.3 g).

In addition, ¹ H-NMR spectrum of _{C-1 (300㎒, CDCl 3} ) is, δ = 8.3 (d, 1H ), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q,

<Synthesis of C-2>

2-Naphthol (20 g) was dissolved in N, N-dimethylacetamide (150 ml). Potassium carbonate (28.7 g) and ethyl 2-bromoacetate (52.2 g) were added and reacted at 100 ° C for 2 hours. Water (300 mL) and ethyl acetate (200 mL) were added to the reaction mixture and the mixture was separated. The organic layer was concentrated, and 48 wt% aqueous sodium hydroxide solution (23 g), ethanol (50 mL) and water (50 mL) . The reaction solution was poured into 1N HCI aqueous solution (500 mL), and the precipitated crystals were filtered and washed with water to obtain a crude carboxylic acid. Then, 30 g of polyphosphoric acid was added and the reaction was carried out at 170 DEG C for 30 minutes. The reaction solution was poured into water (300 mL) and ethyl acetate (300 mL) was added thereto to separate the layers. The organic layer was concentrated and purified by silica gel column chromatography to obtain a ketone compound (10 g).

Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g) and magnesium sulfate (4.5 g) were added to the resulting suspension of the ketone compound (10.0 g) and methanol (100 mL) and the mixture was refluxed for 24 hours. After allowing to cool, water (150 mL) and ethyl acetate (150 mL) were added to separate the layers. The organic layer was separated into four portions of 80 mL of water, concentrated, and then purified by silica gel column chromatography to obtain an oxime compound (5.8 g).

The obtained oxime (3.1 g) was sulfonated as in C-1 to obtain C-2 (3.2 g).

In addition, ¹ H-NMR spectrum of _{C-2 (300㎒, CDCl 3} ) is, δ = 8.3 (d, 1H ), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), (Dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (dd, (ddt, 1H), 1.4-1.2 (m, 8H), 0.8 (t, 3H).

<Synthesis of C-3>

C-3 was synthesized in the same manner as C-1, except that benzenesulfonyl chloride was used instead of p-toluenesulfonyl chloride in C-1.

In addition, ¹ H-NMR spectrum of _{C-3 (300㎒, CDCl 3} ) is, δ = 8.3 (d, 1H ), 8.1 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), (M, 4H), 7.4 (dd, 1H), 7.1 (d, 1H), 5.6 (q, 1H), 1.7 (d, 3H).

D-1: DBA (9,10-dibutoxyanthracene, sensitizer, manufactured by Kawasaki Chemical Industry Co., Ltd.)

E-1: 1,5-diazabicyclo [4.3.0] -5-nonene (basic compound, manufactured by Tokyo Kasei Kogyo Co., Ltd.)

E-2: Compound of the following structure (basic compound, manufactured by Toyo Gosei Co., Ltd.)

F-1: Dyuranate 17B-60PX (block isocyanate compound, manufactured by Asahi Chemical Industry Co., Ltd.)

F-2: Dyuranate MF-K60X (block isocyanate compound, manufactured by Asahi Chemical Industry Co., Ltd.)

G-1: MW-100LM (a melamine compound having a methoxymethyl group on an amino group, manufactured by Sanwa Chemical Co., Ltd.)

G-2: MX-750LM (a melamine compound having a methoxymethyl group on an amino group, manufactured by Sanwa Chemical Co., Ltd.)

H-1: JER150S65 (epoxy compound, manufactured by Mitsubishi Chemical Corporation)

H-2: JER1031S (epoxy compound, manufactured by Mitsubishi Chemical Corporation)

I-1: 3-glycidoxypropyltrimethoxysilane (KBM-403, silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.)

J-1: Megaface F-554 (surfactant, manufactured by DIC Corporation)

&Lt; Measurement of relative dielectric constant &

The photosensitive resin composition was applied to a slit on a bare wafer (N type low resistance) (manufactured by SUMCO), and then prebaked on a hot plate at 90 DEG C for 2 minutes to form a photosensitive resin composition layer having a thickness of 3.0 mu m . The thus-obtained photosensitive resin composition layer was exposed with a PLA-501F exposure apparatus (ultra-high pressure mercury lamp) manufactured by Canon Inc. so that the cumulative irradiation dose was 300 mJ / cm 2 (light intensity: 20 mW / cm 2) Followed by heating for a time to obtain a cured film.

The relative dielectric constant of this cured film was measured using CVmap92A (manufactured by Four Dimensions Inc.) at a measurement frequency of 1 MHz. The results are shown in Table 5.

When this value is 3.6 or less, the relative dielectric constant of the cured film is good.

<Measurement of Swelling Rate>

Each of the photosensitive resin compositions was coated with a slit on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then the solvent was removed by heating on a hot plate at 90 DEG C for 120 seconds to obtain a photosensitive resin To form a composition layer.

The thus-obtained photosensitive resin composition layer was exposed with a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Inc. so that the cumulative irradiation dose was 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) And then heated in an oven at 230 DEG C for 1 hour to obtain a cured film.

The cured film was immersed in NMP at 80 DEG C for 10 minutes, and the film was pulled up to wipe off the liquid on the surface, and the film thickness was immediately measured. The film thickness before immersion and the film thickness after immersion were compared, and the increased ratio was expressed as a percentage. The smaller the value, the better. The results are shown in Table 5 below. The evaluation criteria are as follows.

A, B and C are levels at which there is no practical problem.

A: 100% or more and less than 103%

B: 103% or more and less than 105%

C: 105% or more and less than 110%

D: 110% or more

Swelling rate (%) = film thickness after immersion (占 퐉) / film thickness before immersion (占 퐉) 占 100

&Lt; Evaluation of Panel Display Unevenness &

In the active matrix type liquid crystal display device described in Figs. 1 and 2 of Japanese Patent No. 3321003, a cured film 17 is formed as an interlayer insulating film. The liquid crystal display was allowed to stand in an environment of 60 deg. C and a relative humidity of 80% for 500 hours and then at 25 deg. C for 1 day, and then the panel was energized to observe display irregularities. The results are shown in Table 5.

In the following evaluation, A and B are preferable.

A: An area where display unevenness is not observed is 90% or more

B: a region where display unevenness is not observed is 60% or more and less than 90%

C: a region where display unevenness is not observed is less than 60%

D: Panel display irregularity can not be measured

&Lt; Evaluation of sensitivity &

Each of the photosensitive resin compositions was coated with a slit on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then prebaked on a hot plate at 90 캜 for 120 seconds to volatilize the solvent to obtain a photosensitive resin To form a composition layer.

Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using a PLA-501F exposure device (ultra-high pressure mercury lamp) manufactured by CANON CO., LTD. Then, the exposed photosensitive composition layer was developed with an alkaline developer (0.3 wt% tetramethylammonium hydroxide aqueous solution) at 23 DEG C for 60 seconds, and rinsed with ultrapure water for 20 seconds.

With these operations, the optimum i-line exposure amount (Eopt) when resolving a line-and-space of 13 mu m at a ratio of 1: 1 was taken as sensitivity. The results are shown in Table 5. The evaluation criteria are as follows.

A and B are levels at which there is no practical problem, and C is not preferable from the viewpoint of productivity.

A: Less than 50 mJ / cm 2

B: 50 mJ / cm 2 or more and less than 300 mJ / cm 2

C: 300 mJ / cm 2 or more

[Table 5]

The photosensitive resin composition of the present invention has a high sensitivity, has a low dielectric constant of the resulting cured film, is excellent in resistance to NMP (N-methylpyrrolidone), and can suppress occurrence of panel display irregularity in a reliability test. I could.

The present invention relates to a liquid crystal display device, and more particularly, to a liquid crystal display device and a method of manufacturing the same. 19: ITO transparent electrode, 20: liquid crystal, 22: colored filter, 18: contact hole,

Claims (14)

(Component A) A copolymer comprising at least (a1) a structural unit having a carboxy group protected by an acid-decomposable group, (a2) a structural unit having a crosslinkable group,
(Component B) a copolymer having at least (b1) a structural unit derived from styrene and (b2) a structural unit having a crosslinkable group, and
(Component C) a photoacid generator having a pKa of 4 or less
A positive photosensitive resin composition. The method according to claim 1,
The I / O value obtained by dividing the inorganic value (I) based on the organic conceptual diagram of the component B by the organic value (O) and the I / O value of the polymer in which the carboxyl group of the component A is protected with an acid- Of the positive photosensitive resin composition is 0.40 or less. The method according to claim 1,
Wherein the acid-decomposable group in the constitutional unit (a1) in which the carboxyl group of the component A has a moiety protected by an acid-decomposable group is an acetal. The method according to claim 1,
Wherein the component (A) is a (meth) acrylic copolymer. The method according to claim 1,
Wherein the component C is an oxime sulfonate compound having at least one oxime sulfonate residue represented by the formula (c0).

(In the formula (c0), the broken line indicates a bonding site) The method according to claim 1,
Wherein the component C is a compound represented by the formula (OS-3), the formula (OS-4), the formula (OS-5) or the formula (c3).

Wherein R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ² independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ¹ represents an alkyl group, an aryl group or a heteroaryl group, ⁶ represents independently a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, and m represents 0 to 6 Lt; / RTI &gt;

(In the formula (c3), R ^B1 represents an alkyl group, an alkoxy group, or a halogen atom, and R ^B2 represents an alkyl group or an aryl group) The method according to claim 1,
Wherein the positive photosensitive resin composition further contains a block isocyanate compound. The method according to claim 1,
A positive photosensitive resin composition further comprising an alkoxymethyl group-containing crosslinking agent. (1) a coating step of applying the positive-working photosensitive resin composition according to any one of claims 1 to 8 onto a substrate,
(2) an exposure step of exposing the applied photosensitive resin composition by an actinic ray,
(3) a developing step of developing the exposed photosensitive resin composition with an aqueous developing solution, and
(4) A post-baking step of thermally curing the developed photosensitive resin composition. 10. The method of claim 9,
And a step of exposing the developed photosensitive resin composition to the whole surface after the development step and before the post-baking step. A cured film formed by the method according to claim 9. 12. The method of claim 11,
A cured film which is an interlayer insulating film. An organic EL display device comprising the cured film according to claim 11. A liquid crystal display device comprising the cured film according to claim 11.

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