TWI570508B - Radiation-sensitive composition, cured film, color filter, method for manufacturing cured film, method for manufacturing color filter, solid state imaging component, liquid crystal display device and organic electroluminescence display device - Google Patents

Description

Radiation-sensitive composition, cured film, color filter, method for producing cured film, method for producing color filter, solid-state imaging device, liquid crystal display device, and organic electroluminescence display device

The present invention relates to a radiation sensitive composition, a color filter formed using the radiation sensitive composition, and a method of producing a color filter. In addition, the present invention relates to a solid-state imaging device (particularly a complementary metal oxide semiconductor (CMOS) sensor, an organic CMOS sensor) having the above color filter, a liquid crystal display device, or an organic battery. Electroluminescence (EL) display device.

The composition of the coloring layer of the color filter used in the image sensor or the like has been studied since the past. For example, in Patent Document 1 and Patent Document 2, the rectangularity of the lift pattern and the reduction of the residue have been studied. On the other hand, In Patent Document 3, solvent resolubility, surface smoothness, and improvement of scum of the resist have been studied.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-49029

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-78729

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2006-161035

Here, the requirements for color filters have become strict, and there is a tendency to further reduce the residue and improve the dimensional stability.

In addition, there are cases where exposure or development is performed not only immediately after the preparation of the radiation sensitive composition, but also after exposure (post exposure delay (PED)). In this case, as a result of research by the present inventors, it has been found that there is a tendency that the line width becomes thick.

The present invention has an object of solving the above problems, and an object of the invention is to provide a feeling of having less residue, excellent dimensional uniformity, and less variation in line width after delay after exposure, when a cured film (for example, a color filter or the like) is formed. Radiation linear composition.

As a result of research conducted by the inventors of the present invention, it has been found that the above problems are solved by using a specific polymer and a polymerizable compound in combination. In the present invention, by using a specific polymer and a polymerizable compound in combination, the development speed of the composition can be increased, and as a result, the residue can be successfully reduced or the dimensional uniformity can be improved when the cured film is formed. Further, it is also successful to provide a phase separation in the composition (phase Separation) A radiation-sensitive linear composition in which the line width after the delay is increased to a small amount when the cured film is formed.

Specifically, the above problem is preferably solved by <2> to <10> by the following <1>.

<1> A radiation sensitive composition comprising a polymer, a polymerizable compound, and a polymerization initiator, and comprising a polymerization obtained by polymerizing a monomer component containing a compound represented by the following formula (ED) The polymer contains, as the above polymer, a (meth) acrylate compound having an acid group and a difunctional or higher functional group as the above polymerizable compound.

(In the general formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent)

(2) The radiation sensitive composition according to the above aspect, wherein the ratio of the (meth) acrylate compound having an acid group and having a difunctional or higher value (having an acid group and two) with respect to the total amount of the polymer The functional (meth) acrylate compound/all polymers × 100) is in the range of 1% by mass to 50% by mass.

<3> A radiation sensitive composition as described in <1> or <2>, which is more A polymerizable compound other than the (meth) acrylate compound having an acid group and having a difunctional or higher functional group is contained as the above polymerizable compound.

<4> The radiation-sensitive composition according to <3>, wherein the ratio of the (meth) acrylate compound having an acid group and having a difunctional or higher functional group among the polymerizable compounds is 1% by mass to 50% by mass.

The radiation sensitive composition according to any one of <1> to <4> further comprising at least 1 selected from the group consisting of an ultraviolet absorber, a solvent, a adhesion improver, a polymerization inhibitor, and a surfactant. Kind.

<6> A cured film formed by curing the radiation sensitive composition according to any one of <1> to <5>.

<7> A color filter comprising a coloring layer formed by curing the radiation sensitive composition according to any one of <1> to <5>.

<8> A method for producing a cured film, comprising: (1) a step of applying the radiation-sensitive composition according to any one of <1> to <5> to a substrate; (2) a step of exposing the above-described radiation sensitive composition to be applied; (3) a step of developing the exposed radiation sensitive composition; and (4) thermally hardening the developed radiation sensitive composition Post-baking step.

<9> A method of producing a color filter, comprising: (1) the radiation-sensitive linear composition according to any one of <1> to <5> a step for the substrate; (2) a step of exposing the above-described radiation sensitive composition to be applied; (3) a step of developing the exposed radiation sensitive composition; and (4) developing the same The subsequent radiation-sensitive composition is subjected to a post-baking step of thermal hardening.

<10> A solid-state imaging device, a liquid crystal display device, or an organic EL display device, comprising the color filter according to <7> or a color filter manufactured by the manufacturing method according to <9>.

According to the present invention, it is possible to provide a radiation-sensitive composition having less residue, excellent dimensional uniformity, and little change in line width after delay after exposure.

100‧‧‧Photographic components

101‧‧‧Substrate

102‧‧‧Insulation

103‧‧‧Connecting electrode

104‧‧‧pixel electrodes

105, 106‧‧‧Connecting Department

107‧‧‧Organic layer

108‧‧‧ opposite electrode

109‧‧‧buffer layer

110‧‧‧ Sealing layer

111‧‧‧Color filters

112‧‧‧ partition wall

113‧‧‧Lighting layer

114‧‧‧Protective layer

115‧‧‧ Counter electrode voltage supply unit

116‧‧‧Readout circuit

121‧‧‧Vertical drive

122‧‧‧ Timing generator

123‧‧‧Signal Processing Circuit

124‧‧‧ horizontal drive

125‧‧‧LVDS

126‧‧‧Sequence Conversion Department

127‧‧‧ solder pads

R1‧‧‧1st area

FIG. 1 is a schematic cross-sectional view showing a configuration of a laminated imaging element (organic CMOS).

FIG. 2 is a view showing an example of the overall configuration of a peripheral circuit including the imaging element shown in FIG. 1.

Fig. 3 is a conceptual diagram showing a central portion and an end portion of a square pixel in one shot.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit.

In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acryloyl group" means propylene. Mercapto and methacrylonitrile. In addition, in this specification, "monomer" has the same meaning as "polymerizable compound". The monomer in the present invention is different from the oligomer and the polymer, and means a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group means a group which participates in a polymerization reaction.

In addition, in the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In addition, in the present specification, the viscosity value means a value at 25 °C.

The radiation sensitive composition of the present invention (hereinafter sometimes referred to as "the composition of the present invention"), a cured film, a color filter, a solid-state imaging element (for example, a CMOS sensor, an organic CMOS sensor), and a liquid crystal A display device, an organic EL display device, a method for producing a cured film, a solid-state imaging device, a liquid crystal display device, or a method for producing an organic EL display device will be described in detail. The description of the constituent elements described below may be performed based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

The composition of the present invention is characterized by comprising a polymer and a polymerizable compound And a polymerization initiator comprising a polymer obtained by polymerizing a monomer component containing a compound represented by the following formula (ED) as the polymer, and having an acid group and a difunctional or higher group (A) The acrylate compound is used as the above polymerizable compound.

(In the general formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent)

Hereinafter, the details will be described.

<polymer>

The composition of the present invention contains a polymer obtained by polymerizing a monomer component containing a compound represented by the following formula (ED).

(In the general formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent)

The composition of the present invention can form a heat resistant polymer by polymerizing a monomer component containing a compound represented by the general formula (ED) (hereinafter sometimes referred to as "ether dimer"). A hardened coating film which is extremely excellent in properties and extremely excellent in transparency. In the above formula (ED), the hydrocarbon dimer of the above-mentioned ether dimer is not particularly limited as the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ or R ² , and examples thereof include a methyl group. , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-pentyl, stearyl, lauryl, 2-ethylhexyl, etc. An alkyl group; an aryl group such as a phenyl group; a cyclohexyl group, a tert-butylcyclohexyl group, a dicyclopentadienyl group, a tricyclodecanyl group, an isodecyl group, an adamantyl group, a 2-methyl-2-adamantyl group, or the like An alicyclic group; an alkyl group substituted with an alkoxy group such as 1-methoxyethyl or 1-ethoxyethyl; an alkyl group substituted with an aryl group such as a benzyl group or the like. Among these bases, from the viewpoint of heat resistance, a substituent of a primary carbon or a secondary carbon which is hard to be removed by acid or heat such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group is particularly preferable.

Specific examples of the ether dimer include dimethyl-2,2'-[oxobis(methylene)]bis-2-acrylate and diethyl-2,2'-[ Oxobis(methylene)]bis-2-acrylate, di(n-propyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, di(isopropyl) -2,2'-[oxobis(methylene)]bis-2-acrylate, di(n-butyl)-2,2'-[oxobis(methylene)]bis-2- Acrylate, di(isobutyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, di(t-butyl)-2,2'-[oxo-double ( Methylene)]bis-2-acrylate, bis(third amyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(stearyl)-2 , 2'-[oxobis(methylene)]bis-2-acrylate, bis(lauryl)-2,2'-[oxygen Bis(methylene)]bis-2-acrylate, di(2-ethylhexyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, di(1- Methoxyethyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(1-ethoxyethyl)-2,2'-[oxo-double ( Methylene)]bis-2-acrylate, dibenzyl-2,2'-[oxobis(methylene)]bis-2-acrylate, diphenyl-2,2'-[oxo Bis(methylene)]bis-2-acrylate, dicyclohexyl-2,2'-[oxobis(methylene)]bis-2-acrylate, di(t-butylcyclohexyl)- 2,2'-[oxobis(methylene)]bis-2-acrylate, bis(dicyclopentadienyl)-2,2'-[oxobis(methylene)]bis-2 - acrylate, bis(tricycloindenyl)-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(isoindenyl)-2,2'-[oxo double (methylene)] bis-2-acrylate, diamantyl-2,2'-[oxobis(methylene)]bis-2-acrylate, bis(2-methyl-2-gold gang Alkyl)-2,2'-[oxobis(methylene)]bis-2-acrylate. Among them, dimethyl-2,2'-[oxobis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxo-double (sub- Base]] bis-2-acrylate, dicyclohexyl-2,2'-[oxobis(methylene)]bis-2-acrylate, dibenzyl-2,2'-[oxo double ( Methylene)] bis-2-acrylate. These ether dimers may be used alone or in combination of two or more. The structure from which the compound represented by the above formula (ED) is derived may be copolymerized with another monomer.

In the present invention, the constituent unit derived from the ether dimer is preferably 1 mol% to 50 mol% of the whole, more preferably 1 mol% to 20 mol% of the whole.

Other monomers can also be copolymerized with the ether dimer.

Examples of the other monomer copolymerizable with the ether dimer include a monomer for introducing an acid group, a monomer for introducing a radical polymerizable double bond, a monomer for introducing an epoxy group, and And other monomers other than the monomers that can be copolymerized body. These monomers may be used alone or in combination of two or more.

Examples of the monomer for introducing an acid group include a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid, and a monomer having a phenolic hydroxyl group such as N-hydroxyphenyl maleimide. A monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride. Among them, (meth)acrylic acid is particularly preferred.

Further, the monomer to which the acid group is introduced may be a monomer which can impart an acid group after the polymerization, and examples thereof include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, and a (meth)acrylic acid shrinkage. A monomer having an epoxy group such as a glyceride or a monomer having an isocyanate group such as 2-isocyanatoethyl (meth)acrylate. When a monomer which can impart an acid group after polymerization is used, it is necessary to carry out a treatment for imparting an acid group after the polymerization. The treatment for imparting an acid group after the polymerization differs depending on the type of the monomer, and examples thereof include the following treatments. In the case of using a monomer having a hydroxyl group, for example, a treatment of adding an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride or maleic anhydride can be mentioned. In the case of using a monomer having an epoxy group, for example, a compound having an amine group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol may be added, or, for example, An acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride or maleic anhydride is added to a hydroxyl group produced by addition of an acid such as (meth)acrylic acid. In the case of using a monomer having an isocyanate group, for example, a treatment of adding a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be mentioned.

When the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) contains a monomer for introducing an acid group, the content ratio of the monomer for introducing the acid group is not particularly limited. , but among all the monomer components, preferably 5 The mass % to 70% by mass, more preferably 10% by mass to 60% by mass.

Examples of the monomer to introduce the radically polymerizable double bond include a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid, and a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride. a monomer having an epoxy group such as glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, o- (or m- or m-) vinylbenzyl glycidyl ether Wait. When a monomer for introducing a radical polymerizable double bond is used, it is necessary to carry out a treatment for imparting a radical polymerizable double bond after polymerization. The treatment for imparting a radically polymerizable double bond after the polymerization differs depending on the type of the monomer capable of imparting a radical polymerizable double bond, and examples thereof include the following treatments. When a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid is used, examples thereof include glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate. A treatment of addition of a compound having an epoxy group and a radically polymerizable double bond, such as o- (or m- or p-) vinylbenzyl glycidyl ether. When a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride is used, a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth)acrylate may be used. Addition processing. If using glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, o- (or m- or p-) vinylbenzyl glycidyl ether, etc. In the case of the body, a treatment of adding a compound having an acid group and a radical polymerizable double bond such as (meth)acrylic acid is mentioned.

When a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) contains a monomer for introducing a radical polymerizable double bond, a single one for introducing a radical polymerizable double bond The content ratio of the body is not particularly limited, but Of all the monomer components, it is preferably 5 mass% to 70 mass%, more preferably 10 mass% to 60 mass%.

Examples of the monomer for introducing an epoxy group include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, ortho (or m- or p-)vinyl group. Benzyl glycidyl ether and the like.

When a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) contains a monomer for introducing an epoxy group, the content of the monomer for introducing an epoxy group is not It is particularly limited, but it is preferably 5% by mass to 70% by mass, and more preferably 10% by mass to 60% by mass based on all the monomer components.

Examples of other monomers copolymerizable include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (methyl). ) n-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, (a) (meth) acrylate such as benzyl acrylate or 2-hydroxyethyl (meth) acrylate; aromatic vinyl compound such as styrene, vinyl toluene or α-methyl styrene; N-phenyl cis N-substituted maleimide such as butylene diimide, N-cyclohexyl maleimide, butadiene or substituted butadiene compound such as butadiene or isoprene; Ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride and acrylonitrile; vinyl esters such as vinyl acetate. Among these, from the viewpoint of good transparency and difficulty in impairing heat resistance, methyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and styrene are preferable.

When a monomer component containing a compound represented by the general formula (ED) is allowed to be carried out When the polymer to be polymerized contains another monomer which can be copolymerized, the content ratio of the other copolymerizable monomer is not particularly limited, but is preferably 95% by mass or less, and more preferably 85% by mass or less.

When the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) has an acid group, the acid value is preferably from 30 mgKOH/g to 500 mgKOH/g, more preferably 50 mgKOH/ G~400 mgKOH/g.

A polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) can be easily obtained by polymerizing the above monomer having at least an ether dimer as an essential component. At this time, the cyclization reaction of the ether dimer proceeds simultaneously with the polymerization to form a tetrahydropyran ring structure.

The polymerization method for synthesizing a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) is not particularly limited, and various conventionally known polymerization methods can be employed, and it is particularly preferable to use Solution polymerization. Specifically, for example, a monomer component containing a compound represented by the general formula (ED) can be synthesized by a method for synthesizing the polymer (a) described in JP-A-2004-300204. Polymer.

Hereinafter, an exemplary compound of a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) is shown, but the present invention is not limited to the above-exemplified compounds. The composition ratio of the exemplified compounds shown below is mol%.

[Chemical 4]

[Chemical 5]

In the present invention, it is particularly preferred to use dimethyl-2,2'-[oxobis(methylene)]bis-2-acrylate (hereinafter referred to as "DM") or benzyl methacrylate (hereinafter referred to as It is called "BzMA"), methyl methacrylate (hereinafter referred to as "MMA"), methacrylic acid (hereinafter referred to as "MAA"), and glycidyl methacrylate (hereinafter referred to as "GMA"). The resulting polymer. Tejia is DM: BzMA: MMA: MAA: The molar ratio of GMA is 5~15:40~50:5~15:5~15:20~30. It is preferable that 95% by mass or more of the components constituting the copolymer used in the present invention are the components. Further, the weight average molecular weight of the above polymer is preferably from 9000 to 20,000.

The polymer used in the present invention is not particularly limited, but the weight average molecular weight (by gel) from the viewpoint of the viscosity of the coloring radiation-sensitive composition and the heat resistance of the coating film formed of the composition. The polystyrene equivalent value measured by Gel Permeation Chromatography (GPC) is preferably 1000 to 2 × 10 ⁵ , more preferably 2,000 to 1 × 10 ⁵ , and still more preferably 5,000 to 5 × 10 ⁴ .

The composition of the present invention preferably contains a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) at a ratio of 50% by mass or more of all the polymer components, and more preferably The ratio of 80% by mass or more includes a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED), and more preferably contained in a ratio of 95% by mass or more to contain a compound (ED). A polymer obtained by polymerizing a monomer component of the compound represented. The composition of the present invention is particularly preferably a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED).

The composition of the present invention may contain only one type of the above polymer, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is the above range.

The composition of the present invention may contain a polymer other than the above polymer (hereinafter sometimes referred to as "other polymer"). As the other polymer, an alkali-soluble resin (hereinafter sometimes referred to as "other alkali-soluble resin") is suitable. The other alkali-soluble resin is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, and availability.

The alkali-soluble resin may have at least one base which promotes alkali solubility and is a linear organic high molecular polymer from a molecule (preferably a molecule in which an acrylic copolymer or a styrene copolymer is used as a main chain). Suitable for selection of alkali soluble resin Choose. From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin is preferable, and the viewpoint of controlling developability is preferable. In particular, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin is preferable.

Examples of the base which promotes alkali solubility (hereinafter, also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and are preferably soluble in a solvent and can be developed by a weakly basic aqueous solution. As a base, (meth)acrylic acid is mentioned as a very good. These acid groups may be used alone or in combination of two or more.

The monomer having an acid group after the polymerization is, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or a monomer having an epoxy group such as glycidyl (meth)acrylate. A monomer having an isocyanate group such as 2-isocyanatoethyl (meth)acrylate. These monomers for introducing an acid group may be used alone or in combination of two or more. When an acid group is introduced into an alkali-soluble resin, for example, a monomer having an acid group and/or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as "a monomer for introducing an acid group" may be used. ") It is sufficient to carry out polymerization as a monomer component. Further, when a monomer capable of imparting an acid group after polymerization is introduced as an acid group as a monomer component, a treatment for imparting an acid group as described later is required after the polymerization.

For the production of an alkali-soluble resin, for example, a method using a known radical polymerization method can be applied. The polymerization conditions such as the temperature, the pressure, the type and amount of the radical initiator, and the type of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by a person skilled in the art, and experimental conditions can be specified.

As the linear organic high molecular polymer used as the alkali-soluble resin, it is preferably Examples of the polymer having a carboxylic acid in the side chain include a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified maleic acid. An alkali-soluble phenol resin such as an acid copolymer or a novolac type resin, and an acid cellulose derivative having a carboxylic acid in a side chain and a polymer obtained by adding a hydroxyl group to an acid anhydride. Copolymers of (meth)acrylic acid with other monomers copolymerizable therewith are particularly suitable as alkali-soluble resins. Examples of the other monomer copolymerizable with (meth)acrylic acid include an alkyl (meth)acrylate, an aryl (meth)acrylate, and a vinyl compound. Examples of the (meth)acrylic acid alkyl ester and the (meth)acrylic acid aryl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate Examples of esters, toluene (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like, and examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, and A. Glycidyl acrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc., as Japan The N-substituted maleimide monomer described in Japanese Laid-Open Patent Publication No. Hei 10-300922, the N-phenyl maleimide, N-cyclohexyl maleimide Wait. Further, these other monomers copolymerizable with (meth)acrylic acid may be used alone or in combination of two or more.

In the present invention, an alkali-soluble phenol resin can also be preferably used. Examples of the alkali-soluble phenol resin include a novolak resin and a vinyl polymer.

The novolac resin is obtained by, for example, condensing a phenol with an aldehyde in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethyl phenol, butyl phenol, xylenol, phenylphenol, catechol, resorcin, gallic phenol, naphthol, or bisphenol A. .

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, and benzaldehyde.

The phenols and aldehydes may be used singly or in combination of two or more.

Specific examples of the novolac resin include, for example, meta-cresol, para-cresol, or a condensation product of a mixture of these and formalin.

The above novolac resin can also be adjusted by a method such as fractionation to adjust the molecular weight distribution. Further, a low molecular weight component having a phenolic hydroxyl group such as bisphenol C or bisphenol A may be mixed with the novolak resin.

Further, in order to improve the crosslinking efficiency of the composition in the present invention, an alkali-soluble resin having a polymerizable group may also be used. The alkali-soluble resin having a polymerizable group is useful as an alkali-soluble resin such as an allyl group, a (meth)acryl group, or an allyloxyalkyl group in the side chain. Examples of the polymer containing the above polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.) and Photomer 6173 (polyurethane acrylic oligomer containing COOH, diamonds). Clover Co., Ltd. (manufactured by Diamond Shamrock Co., Ltd.), Viscoat R-264, KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Placcel The CF200 series (both manufactured by Daicel Chemical Industry Co., Ltd.) and Ebecryl 3800 (manufactured by Daicel-UCB Co., Ltd.). The alkali-soluble resin containing a polymerizable group is preferably a resin containing a polymerizable double bond modified by a urethane, and reacting an isocyanate group with an OH group in advance. Obtaining an unreacted isocyanate group and a compound containing a (meth)acryloyl group and reacting with a carboxyl group-containing acrylic resin; and having an epoxy group and a polymerizable double in the molecule by an acrylic resin containing a carboxyl group; An unsaturated group-containing acrylic resin obtained by the reaction of a bond compound; an acid pendant group type epoxy acrylate resin; and an OH group-containing acrylic resin reacted with a dibasic acid anhydride having a polymerizable double bond An acrylic resin containing a polymerizable double bond; a resin obtained by reacting an OH group-containing acrylic resin with an isocyanate and a compound having a polymerizable group; and Japanese Patent Laid-Open No. 2002-229207, and Japanese Patent A tree having a leaving group such as a halogen atom or a sulfonate group and having an ester group in a side chain at the α-position or the β-position described in JP-A-2003-335814 Alkaline treatment of the resin obtained.

Further, it is also preferred to use (a) polyimine, polybenzoxazole or a precursor thereof as the alkali-soluble resin. Polyimine and polybenzoxazole are resins having a cyclic structure of a quinone ring or an oxazole ring in a main chain structure. The polyimidazole precursor and the polybenzoxazole precursor are resins having a guanamine bond in the main chain, and are subjected to dehydration ring closure by heat treatment or chemical treatment, thereby becoming the above polybendimimine or polybenzazole Oxazole. By containing these resins, a composition excellent in insulation properties can be obtained. Examples of the polyimine precursor include polyglycine, polyamidomate, and polyamidite. Amine, polyisophthalimide, and the like. Examples of the polybenzoxazole precursor include polyhydroxyguanamine, polyamine amide, polyamine, and polyamidoximine. Preferably, the number of repeats of the structural unit is from 10 to 100,000. Two or more kinds of these compounds may be contained, and a copolymer having two or more kinds of structural units of these compounds may be contained. When the curing is carried out by heat treatment at a low temperature of 250 ° C or lower, it is more preferably polyimine from the viewpoint of chemical resistance.

Polyimine is usually obtained by dehydration ring closure of polylysine by chemical treatment by heating or acid or alkali, and has a tetracarboxylic acid residue and a diamine residue, and the above polyamine is made of four One of the polyimine precursors obtained by reacting a carboxylic acid dianhydride with a diamine.

In the present invention, the polyimine is preferably a structural unit represented by the following formula (3). Two or more types of the above structural unit may be contained, and a copolymer with other structural units may be used.

In the above formula (3), R ¹ -(R ³ ) _p represents a tetracarboxylic acid residue. R ¹ is a tetravalent to 10-valent organic group, and preferably a tetravalent to 10-valent organic group having an aromatic ring or a cyclic aliphatic group and having 5 to 40 carbon atoms.

Examples of the acid dianhydride constituting the tetracarboxylic acid residue include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,3,3',4'. -biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 2,2 ',3,3'-diphenyl ketone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl) Propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, double (3,4) -dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, bis(3,4-dicarboxyphenyl) Ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)decanoic acid dianhydride, 9,9-double {4-(3) , 4-dicarboxyphenoxy)phenyl}decanoic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4 , 9,10-fluorene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid An aromatic tetracarboxylic dianhydride such as a dianhydride or an acid dianhydride having the structure shown below, or butane tetracarboxylic dianhydride, 1, 2, 3 An aliphatic tetracarboxylic dianhydride such as 4-cyclopentanetetracarboxylic dianhydride. Two or more kinds of the above acid dianhydrides can be used.

R ¹⁰ represents an oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ . R ¹¹ and R ¹² represent a hydrogen atom, a hydroxyl group or a thiol group.

In the above formula (3), R ² -(R ⁴ ) _q represents a diamine residue. R ² is a divalent to octavalent organic group, and preferably a divalent to octavalent organic group having an aromatic ring or a cyclic aliphatic group and having 5 to 40 carbon atoms.

Examples of the diamine constituting the diamine residue include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and 3,4'-diaminodiphenylmethane. , 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene, 3,4'-diaminodiphenyl Thioether, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1, 5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)fluorene, bis(3-aminophenoxyphenyl)fluorene, bis(4-aminophenoxyl) Biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4, 4'-Diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3 , 3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4 , 4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis (4 -aminophenyl)anthracene or a compound obtained by substituting at least a part of hydrogen atoms of the aromatic rings with an alkyl group or a halogen atom, or a cyclohexyl group An aliphatic diamine such as a diamine or methylene dicyclohexylamine; and a diamine having the structure shown below. Two or more kinds of the above diamines can be used.

[化8]

R ¹⁰ represents an oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ . R ¹¹ to R ¹⁴ represent a hydrogen atom, a hydroxyl group or a thiol group.

Polybenzoxazole can be obtained by reacting a bisaminophenol with a dicarboxylic acid, a corresponding dicarbonyl chloride, an active dicarboxylic acid ester or the like. Generally, it can be obtained by subjecting polyhydroxyguanamine to dehydration ring closure by chemical treatment by heating or acid or phosphoric anhydride, a base, a carbodiimide compound or the like, and having a dicarboxylic acid residue and a bisaminophenol residue. The above polyhydroxyguanamine is one of polybenzoxazole precursors obtained by reacting a bisaminophenol compound with a dicarboxylic acid.

Examples of the acid constituting the dicarboxylic acid residue include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, and diphenyl. Keto dicarboxylic acid, triphenyl dicarboxylic acid, and the like. Two or more kinds of the above acids can be used.

Examples of the diamine constituting the bisaminophenol residue include a diamine having the structure shown below. Two or more kinds of the above diamines can be used.

[Chemistry 9]

R ¹⁰ represents an oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ . R ¹¹ to R ¹⁴ represent a hydrogen atom, a hydroxyl group or a thiol group, and at least one of each diamine is a hydroxyl group.

The polyimine precursor can be obtained, for example, by reacting a tetracarboxylic dianhydride (a part of which may be substituted into an acid anhydride, a monofluorinated chlorine compound or a mono-active ester compound) with a diamine compound, and having a tetracarboxylic acid residue and two Amine residue.

The polybenzoxazole precursor can be obtained, for example, by reacting a bisaminophenol compound with a dicarboxylic acid, and has a dicarboxylic acid residue and a bisaminophenol residue.

In the present invention, the polyimidazole precursor and the polybenzoxazole precursor are preferably those having a structural unit represented by the following formula (4). Two or more types of the above structural unit may be contained, and a copolymer with other structural units may be used.

[化10]

In the above formula (4), R ⁵ and R ^{6 each} represent a divalent to octavalent organic group, and may be the same or different. R ⁷ and R ⁸ represent a phenolic hydroxyl group, a sulfonic acid group, a thiol group, or COOR ⁹ , and may be the same or different. R ⁹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. r and s represent integers from 0 to 6. Where r+s>0.

In the above formula (4), R ⁵ -(R ⁷ ) _r represents an acid residue such as a dicarboxylic acid or a tetracarboxylic acid. R ⁵ is a divalent to octavalent organic group, and preferably a divalent to octavalent organic group having an aromatic ring or a cyclic aliphatic group and having 5 to 40 carbon atoms.

Examples of the acid constituting the acid residue include, as an example of the dicarboxylic acid, an acid which is a dicarboxylic acid residue constituting the polybenzoxazole. Examples of the tricarboxylic acid include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid. Examples of the tetracarboxylic acid include pyromellitic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2. ',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-diphenyl ketone tetracarboxylic acid, 2,2',3,3'-diphenyl ketone tetracarboxylic acid, 2 ,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxybenzene Ethylene, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, double (3,4-dicarboxyphenyl)anthracene, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid , 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-decanetetracarboxylic acid, and tetracarboxylic acid having the structure shown below An aromatic tetracarboxylic acid, or an aliphatic tetracarboxylic acid such as butanetetracarboxylic acid or 1,2,3,4-cyclopentanetetracarboxylic acid. Two or more kinds of the above acids can be used.

R ¹⁰ represents an oxygen atom, C(CF ₃ ) ₂ , C(CH ₃ ) ₂ or SO ₂ . R ¹¹ and R ¹² represent a hydrogen atom, a hydroxyl group or a thiol group.

Among these, one or two carboxyl groups in the tricarboxylic acid and the tetracarboxylic acid correspond to the R ⁷ group in the formula (4). Further, it is more preferred to substitute one or four of the above-exemplified dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acids by using a R ⁷ group in the formula (4), preferably a hydroxyl group or a sulfonic acid group, a thiol group or the like. The hydrogen atom is the one. These acids can be used as they are or as an acid anhydride or an active ester.

R ⁶ -(R ⁸ ) _s in the above formula (4) represents an amine residue such as a diamine or a bisaminophenol. R ⁸ is a divalent to octavalent organic group, and preferably a divalent to octavalent organic group having an aromatic ring or a cyclic aliphatic group and having 5 to 40 carbon atoms.

Examples of the diamine constituting the amine residue include those exemplified as the diamine constituting the diamine residue of the polyimine.

Further, it is preferred to block the ends of the resins by a monoamine having an hydroxyl group, a carboxyl group, a sulfonic acid group or a thiol group, an acid anhydride, a hydrazine chloride or a monocarboxylic acid. Two or more kinds of the above resins can be used. Easily by having the above-mentioned group at the end of the main chain The dissolution rate of the resin to the alkaline aqueous solution is adjusted to a preferred range. Preferred examples of the monoamine include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, and 1-hydroxy-5-amino group. Naphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-amino group Naphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-amino group Naphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-amine Benzobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-amino group Phenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, and the like. Two or more kinds of the above monoamines can be used.

Preferable examples of the acid anhydride, hydrazine chloride, and monocarboxylic acid include phthalic anhydride, maleic anhydride, nadic acid, cyclohexane dicarboxylic anhydride, and 3-hydroxyphthalic acid. Anhydride such as acetic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5 -monocarboxylic acids such as carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, and the like a monoterpene chlorine compound obtained by hydrazine hydration of a carboxyl group, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6- a monoterpene chlorine compound obtained by chlorination of only one carboxyl group of a dicarboxylic acid such as dicarboxynaphthalene, 1,7-dicarboxynaphthalene or 2,6-dicarboxynaphthalene by a hydrazine monochloride compound and an N-hydroxyl group An active ester compound obtained by the reaction of benzotriazole or N-hydroxy-5-northene-2,3-dicarboxy quinone. Two or more kinds of the above acid anhydride, hydrazine chloride, and monocarboxylic acid can be used.

As the alkali-soluble resin, a polyvalent copolymer containing a benzyl (meth)acrylate/(meth)acrylic copolymer or a benzyl (meth)acrylate/(meth)acrylic acid/other monomer is particularly suitable. In addition, the 2-hydroxypropyl (meth)acrylate/polystyrene described in JP-A-7-140654 is exemplified by the copolymerization of 2-hydroxyethyl methacrylate. Molecular monomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromer / benzyl methacrylate / methacrylic acid copolymer , 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromer/methyl Benzyl acrylate/methacrylic acid copolymer and the like.

The acid value of the alkali-soluble resin is preferably from 30 mgKOH/g to 200 mgKOH/g, more preferably from 50 mgKOH/g to 150 mgKOH/g, most preferably from 70 mgKOH/g to 120 mgKOH/g.

Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, most preferably 7,000 to 20,000.

In the present invention, the content of all the polymers in the radiation sensitive composition is preferably from 10% by mass to 90% by mass based on the total solid content of the radiation sensitive composition from the viewpoint of developability and the like. Preferably, it is 20% by mass to 60% by mass, and particularly preferably 30% by mass to 50% by mass. Further, in the present invention, the total solid content of the radiation sensitive composition means all components after removal of the solvent.

<Polymerizable compound>

The composition of the present invention contains at least an acid group and a difunctional or higher (A) The acrylate compound is used as a polymerizable compound.

The (meth) acrylate compound having an acid group and having a difunctional or higher functional group is preferably represented by the following formula (2).

(A) _n1 -L-(Ac) _n2 Formula (2)

(In the formula (2), A represents an acid group, L is a (n1+n2) valent group containing two or more atoms selected from an oxygen atom, a carbon atom and a hydrogen atom, and Ac represents a (meth) propylene group. An alkoxy group; n1 represents an integer of 1 to 3; and n2 represents an integer of 2 or more. A may, for example, be a carboxylic acid group, a sulfonylamino group, a phosphonic acid group or a sulfonic acid group, and is preferably a carboxylic acid group.

L is preferably a group containing at least a carbon atom and a hydrogen atom. The total number of carbon atoms and oxygen atoms constituting L is preferably from 3 to 15, more preferably from 6 to 12.

N1 is preferably 1 or 2, more preferably 1. N2 is preferably an integer of 6 or less, more preferably an integer of 2 to 5, and still more preferably 3 or 4.

In the present invention, the ratio of the (meth) acrylate compound having an acid group and having a difunctional or higher value among all the polymerizable compounds is preferably from 1% by mass to 50% by mass, more preferably from 1% by mass to 20% by mass. .

The (meth) acrylate compound having an acid group and having a difunctional or higher functional group may be used alone or in combination of two or more. When two or more types are included, the total amount thereof becomes the above range.

The composition of the present invention may have a polymerizable compound other than the (meth) acrylate compound having an acid group and a difunctional or higher functional group (hereinafter sometimes referred to as "other polymerizable compound"), and preferably has the polymerization. Sex compounds.

Specific examples of the other polymerizable compound are selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such a group of compounds is widely known in the industrial field, and these compounds can be used without particular limitation in the present invention. The compounds may be, for example, any of a monomer, a prepolymer, that is, a dimer, a trimer, and an oligomer, or a mixture of the above, and a polymer of the above, but are preferably single. body. The polymerizable compound in the invention may be used alone or in combination of two or more.

More specifically, examples of the monomer and the prepolymer thereof include an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or Esters, guanamines, and multimers thereof, preferably esters of an unsaturated carboxylic acid and an aliphatic polyol compound, and guanamines of an unsaturated carboxylic acid and an aliphatic polyamine compound, and Multimer. Further, an unsaturated carboxylic acid ester or a guanamine having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, an addition reaction with a monofunctional or polyfunctional isocyanate or an epoxy group, or A dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid or the like. Further, an addition reaction product of an unsaturated carboxylic acid ester or an oxime amine having an electrophilic substituent such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol, An unsaturated carboxylic acid ester or decylamine having a derivatizing substituent such as a halogen group or a tosyloxy group Substituting reactants with monofunctional or polyfunctional alcohols, amines, thiols are also suitable. Further, as another example, a group of compounds substituted with a vinylbenzene derivative such as an unsaturated phosphonic acid or styrene, a vinyl ether or an allyl ether may be used instead of the above unsaturated carboxylic acid.

As the specific compound, in the present invention, the compound described in Paragraph No. 0095 to Paragraph No. 0108 of JP-A-2009-288705 can also be suitably used.

In addition, as the polymerizable compound, at least one ethylenically unsaturated group-containing compound having at least one ethyl group which can undergo addition polymerization and having a boiling point of 100 ° C or higher at normal pressure is also used as the polymerizable monomer. good. Examples of the compound include monofunctional acrylates or methyl groups such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate. Acrylate; polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tri (propylene oxy group) After the addition of ethylene oxide or propylene oxide to a polyfunctional alcohol, propyl)ether, tris(propyleneoxyethyl)isocyanate, glycerin or trimethylolethane (methyl) The (meth)acrylic acid amine group described in Japanese Patent Laid-Open Publication No. SHO-48-41708, Japanese Patent Publication No. SHO-50-6034, and JP-A-51-37193 Formic acid esters, Japanese Patent Laid-Open No. 48-64183, Japanese Patent Publication No. Sho 49-43191, and Japanese Special The polyester acrylate described in the publication No. 52-30490, a polyfunctional acrylate or methacrylate such as an epoxy acrylate which is a reaction product of an epoxy resin and (meth)acrylic acid, and the like mixture.

A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated group such as glycidyl (meth)acrylate may, for example, be mentioned.

Further, as another preferable polymerizable compound, fluorene as described in JP-A-2010-160418, JP-A-2010-129825, and Japanese Patent No. 4,364,216, etc., may be used. A compound having a bifunctional or higher ethylenic polymerizable group and a cardo resin.

In addition, as a compound having a boiling point of 100 ° C or higher and having at least one ethylenically unsaturated group capable of undergoing addition polymerization under normal pressure, paragraph number 0254 to paragraph 0257 of JP-A-2008-292970 The compounds described in the above are also suitable.

In addition to the above, a radical polymerizable monomer represented by the following formula (MO-1) to formula (MO-5) can be suitably used. Further, in the formula, when T is an alkyloxy group, the terminal on the carbon atom side is bonded to R.

[Chemistry 13]

In the above formula, n is 0 to 14, and m is 1 to 8. One molecule exists A plurality of R and T may be the same or different from each other.

In each of the radical polymerizable monomers represented by the above formula (MO-1) to formula (MO-5), at least one of the plurality of R represents -OC(=O)CH=CH ₂ Or a group represented by -OC(=O)C(CH ₃ )=CH ₂ .

Specific examples of the radically polymerizable monomer represented by the above formula (MO-1) to (MO-5) may be suitably used in the present invention, as disclosed in JP-A-2007-269779. The compound described in Paragraph No. 0248 to Paragraph No. 0251.

The following compounds which are described in the general formula (1) and the general formula (2) together with the specific examples thereof can also be used as a polymerizable compound, which is the above-mentioned polyfunctional alcohol, in the Japanese Patent Publication No. Hei 10-62986. A compound obtained by adding (meth) acrylate to ethylene oxide or propylene oxide.

Among them, as the polymerizable compound, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Japan) are preferred. Chemical Pharmaceutical Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (commercially available) KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and a structure in which the (meth)acrylonyl group is interposed between ethylene glycol and propylene glycol residues. These oligomer types can also be used.

The polymerizable compound may be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. Therefore, as described above, if the ethylenic compound is as mixed In the case of a compound having an unreacted carboxyl group as in the case of the compound, the ethylenic compound can be used as it is, and if necessary, a hydroxyl group of the above-mentioned ethylenic compound can be reacted with a non-aromatic carboxylic anhydride to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic anhydride to be used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylation. Hexahydrophthalic anhydride, succinic anhydride, maleic anhydride.

In the present invention, the monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and preferably an acid having an unreacted hydroxyl group of the aliphatic polyhydroxy compound and a non-aromatic carboxylic anhydride The polyfunctional monomer is particularly preferred in the ester, and the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. As a commercial item, M-510, M-520, etc. which are polyacid-acid-modified acrylic oligomer manufactured by the East Asia Synthetic Co., Ltd. are mentioned, for example.

The preferred acid value of the polyfunctional monomer having an acid group is from 0.1 mg-KOH/g to 40 mg-KOH/g, particularly preferably from 5 mg-KOH/g to 30 mg-KOH/g. When the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are lowered, and if it is too high, production or handling becomes difficult, photopolymerization performance is lowered, and curability such as surface smoothness of a pixel is poor. Therefore, when two or more kinds of polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is necessary to carry out the acid groups of all the polyfunctional monomers into the above range. Adjustment.

Further, as the polymerizable monomer, a polyfunctional monomer having a caprolactone structure is preferable.

As a polyfunctional monomer having a caprolactone structure, as long as it has a molecule The caprolactone structure is not particularly limited, and examples thereof include trimethylolethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, and Ε-caprolactone modified polyfunctional (meth)acrylic acid obtained by esterification of a polyol such as pentaerythritol, tripentaerythritol, glycerin, diglycerin or trimethylol melamine with (meth)acrylic acid and ε-caprolactone ester. Among them, a polyfunctional monomer having a caprolactone structure represented by the following formula (1) is preferred.

(In the formula, all of the six R's are represented by the following formula (2), or one to five of the six R's are represented by the following formula (2), and the remainder is as follows The base represented by the formula (3)

(wherein R ¹ represents a hydrogen atom or a methyl group, m represents an integer of 1 or 2, and " ^* " represents a bond bond)

[化17]

(wherein R ¹ represents a hydrogen atom or a methyl group, and " ^* " represents a bond bond)

The polyfunctional monomer having such a caprolactone structure is, for example, DPCA-20 sold by Nippon Kayaku Co., Ltd. as a KAYARAD DPCA series (in the above formula (1) to formula (3), m= 1. The number of groups represented by the formula (2) = 2, the compound in which R ¹ is a hydrogen atom), DPCA-30 (in the above formula (1) to formula (3), m = 1, by the formula (2) ) groups represented by the number of = 3, R ¹ are hydrogen atoms), DPCA-60 (the above formula (1) to (3), m = 1, by the formula (2) is represented by the group Amount = 6 and a compound in which R ¹ is a hydrogen atom), DPCA-120 (in the above formulas (1) to (3), m = 2, the number of groups represented by the formula (2) = 6, R ¹ Compounds which are all hydrogen atoms) and the like.

In the present invention, the polyfunctional monomer having a caprolactone structure may be used singly or in combination of two or more.

Further, as the specific monomer in the present invention, at least one selected from the group consisting of compounds represented by the following general formula (i) or (ii) is also preferable.

[化18]

In the general formula (i) and Formula (ii), E each independently represent _{- ((CH 2) yCH 2} O) -, or _{- ((CH 2) yCH (} CH 3) O) -, y is independently The ground represents an integer of 0 to 10, and X each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.

In the above formula (i), the total of the acryl fluorenyl group and the methacryl fluorenyl group is three or four, and m each independently represents an integer of 0 to 10, and the total of each m is an integer of from 0 to 40. However, when the total of each m is 0, any one of X is a carboxyl group.

In the above formula (ii), the total of the acrylonitrile group and the methacryl group is 5 or 6, and n each independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the above formula (i), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.

In the above formula (ii), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

Further, -((CH ₂ )yCH ₂ O)- or -((CH ₂ )yCH(CH ₃ )O)- in the formula (i) or the formula (ii) is preferably an end on the oxygen atom side The shape of the knot with X.

The compound represented by the above formula (i) or (ii) may be used alone or in combination of two or more. Particularly preferred is a form in which all six of X in the formula (ii) are an acrylonitrile group.

In addition, the total content of the compound represented by the general formula (i) or the general formula (ii) in a specific monomer is preferably 20% by mass or more, and more preferably 50% by mass or more.

The compound represented by the above formula (i) or formula (ii) can be synthesized by the following steps as a previously known step: ring-opening addition of pentaerythritol or dipentaerythritol with ethylene oxide or propylene oxide The step of reacting the ring-opening skeleton and the step of introducing a (meth)acryl fluorenyl group by reacting a terminal hydroxyl group of the ring-opening skeleton with, for example, (meth)acryloyl chloride. Each step is a well-known step, and a person represented by the formula (i) or the formula (ii) can be easily synthesized by a person skilled in the art.

Among the compounds represented by the above formula (i) and formula (ii), a pentaerythritol derivative and/or a dipentaerythritol derivative are more preferred.

Specifically, a compound represented by the following formula (a) to formula (f) (hereinafter also referred to as "exemplary compound (a) to exemplary compound (f)")), preferably an exemplified compound (a), exemplified compound (b), exemplified compound (e), and exemplified compound (f).

[Chemistry 19]

[Chemistry 20]

As a commercial item of the specific monomer represented by the general formula (i) and the general formula (ii), for example, a tetrafunctional acrylic acid having four ethylene ethoxylate chains can be exemplified by Sartomer Co., Ltd. Ester SR-494, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having 6 pentyloxy chains, TPA as a trifunctional acrylate having 3 extended-butoxy chains -330 and so on.

In addition, as a polymerizable compound, for example, Japanese Patent Publication No. Sho 48-41708, Japanese Patent Laid-Open No. Sho 51-37193, Japanese Patent Publication No. Hei 2-32293, and Japanese Patent Publication No. Hei 2-16765 The urethane amides described, or Japanese Patent Publication No. Sho 58-49860, Japanese Patent A urethane compound having an ethylene oxide skeleton described in Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39418 is also suitable. In addition, an amine-based structure or a sulfide structure is described in the molecule as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. As the polymerizable compound, an addition polymerizable compound can obtain a composition excellent in photospeed.

As a commercial product of a polymerizable compound, urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku Pulp company), UA-7200 (made by Shin-Nakamura Chemical Co., Ltd.) , DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Co., Ltd.).

As the polymerizable compound, a polyfunctional thiol compound having two or more mercapto groups (SH) in the same molecule is also suitable. Particularly preferred is those represented by the following formula (I).

(wherein R ¹ represents an alkyl group, R ² represents an n-valent aliphatic group which may contain an atom other than carbon, R ⁰ represents an alkyl group other than H, and n represents 2 to 4)

Specific examples of the polyfunctional thiol compound represented by the above formula (I) include 1,4-bis(3-mercaptobutyloxy)butane having the following structural formula [Formula (II) )], 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione [Formula (III) ], and pentaerythritol tetrakis(3-mercaptobutyrate) [formula (IV)] and the like. These polyfunctional thiols may be used alone or in combination of two or more.

The amount of the polyfunctional thiol in the composition is desirably 0.3% by weight to 8.9% by weight, more preferably 0.8% by weight to 6.4% by weight based on the total solid content other than the solvent. Range to add. By adding multiple officials The thiol can improve the stability, odor, sensitivity, resolution, developability, adhesion, and the like of the composition.

The details of the structure, the use alone or in combination, and the amount of use of the polymerizable compounds can be arbitrarily set in combination with the final performance design of the composition. For example, from the viewpoint of sensitivity, a structure having a large content of an unsaturated group per molecule is preferable, and in many cases, a difunctional or higher is preferable. Moreover, from the viewpoint of improving the strength of the colored cured film, a trifunctional or higher polymerizable compound is preferable, and further, a different functional group number is used in combination. A method of adjusting both sensitivity and strength of a polymerizable compound of a different polymerizable group (for example, an acrylate, a methacrylate, a styrene compound, or a vinyl ether compound) is also effective. Further, it is preferable to use a polymerizable compound having a trifunctional or higher functional group and a different ethylene oxide chain length to adjust the developability of the composition, and to obtain an excellent pattern forming ability. Further, the compatibility and dispersibility of other components (for example, a photopolymerization initiator, a colorant (pigment), a binder polymer, etc.) contained in the composition, the selection and use of the polymerizable compound It is also an important factor. For example, low-purity compounds or two or more types may be used in combination to improve compatibility. Further, from the viewpoint of improving the adhesion to a hard surface such as a substrate, it is sometimes possible to select a specific structure.

The other polymerizable compound in the composition of the present invention is preferably 80% by mass or less, more preferably 60% by mass or less, still more preferably 40% by mass or less. In the present invention, as the other polymerizable compound, a (meth) acrylate having no acid group is particularly preferable, and a polyfunctional (meth) acrylate having no acid group is more preferable. In the present invention, it is preferred to have an acid group and a difunctional or higher (meth) acrylate and not The total amount of the acid group-containing (meth) acrylate accounts for 80% by mass or more of all the polymerizable compounds.

The composition of the present invention has a ratio of an acid group and a difunctional or higher (meth) acrylate (an acid group and a difunctional or higher (meth) acrylate/all polymer) based on the total amount of the polymer. ×100 (% by mass) is preferably 1% by mass to 50% by mass, more preferably 3% by mass to 30% by mass, still more preferably 5% by mass to 20% by mass, and still more preferably 5% by mass to 15% by mass. quality%. By setting it as such a range, there exists a tendency for the residue to further reduce.

<Polymerization initiator>

The composition of the present invention comprises a polymerization initiator. The polymerization initiator is not particularly limited as long as it has a function of starting polymerization of the polymerizable compound, and can be appropriately selected from known polymerization initiators. For example, it is preferred that the ultraviolet region has a sensitivity to visible light. Further, it may be an active agent which generates a living radical with a light excitation sensitizer, and may also be an initiator which starts cationic polymerization corresponding to the kind of the monomer.

Further, the above polymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in a range of from about 300 nm to 800 nm, more preferably from 330 nm to 500 nm.

Examples of the polymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton or a oxadiazole skeleton), a mercaptophosphine compound such as a mercaptophosphine oxide, a hexaarylbiimidazole, or an anthracene derivative. An isomer compound, an organic peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, Hydroxyacetophenone and the like.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include a compound described in Japanese Society of Chemical Engineering, Bull. Chem. Soc. Japan, 42, 2924 (1969), and British Patent No. 1388492. The compound described in the specification, the compound described in JP-A-53-133428, the compound described in the specification of German Patent No. 3337024, and the Journal of Organic Chemistry (J. Org) by Schaefer et al. a compound described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The compound described in the publication No. 5-34920, and the compound described in the specification of U.S. Patent No. 4,212,976.

Examples of the compound described in the above specification of U.S. Patent No. 4,212,976 include compounds having an oxadiazole skeleton (e.g., 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5-(4-chlorophenyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole , 2-trichloromethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2 -tribromomethyl-5-(2-naphthyl)-1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2- Trichloromethyl-5-(4-chlorostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-methoxystyryl)-1,3, 4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-n-butoxystyrene Base)-1,3,4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4-oxadiazole, etc.).

Further, examples of the polymerization initiator other than the above include acridine derivatives. (eg, 9-phenyl acridine, 1,7-bis(9,9'-acridinyl)heptane, etc.), N-phenylglycine, etc., polyhalogen compounds (eg, carbon tetrabromide, benzene) Tris-bromomethyl hydrazine, phenyl trichloromethyl ketone, etc.), coumarin (eg 3-(2-benzofuranyl)-7-diethylamino coumarin, 3- (2-benzofurancarbenyl)-7-(1-pyrrolidinyl)coumarin, 3-benzylidinyl-7-diethylaminocoumarin, 3-(2-methoxybenzene Mercapto)-7-diethylaminocoumarin, 3-(4-dimethylaminobenzimidyl)-7-diethylamine coumarin, 3,3'-carbonyl bis (5, 7-di-n-propoxycoumarin), 3,3'-carbonylbis(7-diethylaminocoumarin), 3-benzylidene-7-methoxycoumarin, 3- (2-furanylmethyl)-7-diethylaminocoumarin, 3-(4-diethylaminocinnamate)-7-diethylamine coumarin, 7-methoxy-3 -(3-pyridylcarbonyl)coumarin, 3-benzylidene-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, in addition, Japanese patent Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2002-363206 The coumarin compound or the like described in JP-A-2002-363208, JP-A-2002-363209, and the like, and fluorenylphosphine oxides (for example, bis(2,4,6-trimethylbenzene) Mercapto)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphenylphosphine oxide, LucirinTPO, etc., metallocenes ( For example, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, η5-cyclopentane Alkenyl-n-hexa-cumyl-iron (1+)-hexafluorophosphate (1-), etc., Japanese Patent Laid-Open No. Sho 53-133428, Japanese Patent Publication No. Sho 57-1819 The compound described in Japanese Patent Publication No. Sho 57-6096, and the specification of U.S. Patent No. 3,615,455.

Examples of the ketone compound include diphenyl ketone and 2-methyl bis. Phenyl ketone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 4-methoxydiphenyl ketone, 2-chlorodiphenyl ketone, 4-chlorodiphenyl ketone, 4- Bromodiphenyl ketone, 2-carboxydiphenyl ketone, 2-ethoxycarbonyldiphenyl ketone, diphenyl ketone tetracarboxylic acid or its tetramethyl ester, 4,4'-bis(dialkylamino group) Diphenyl ketones (eg 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(dicyclohexylamino)diphenyl ketone, 4,4'-double ( Diethylamino)diphenyl ketone, 4,4'-bis(dihydroxyethylamino)diphenyl ketone, 4-methoxy-4'-dimethylaminodiphenyl ketone, 4,4' -dimethoxydiphenyl ketone, 4-dimethylaminodiphenyl ketone, 4-dimethylaminoacetophenone, benzil, oxime, 2-tert-butyl fluorene, 2-methylindole, phenanthrenequinone, xanthone, thioxanthone, 2-chloro-thiaxanone, 2,4-diethylthiazinone, anthrone, 2-benzyl -dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1 - Acetone, 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomer, benzoin, benzoin ether (eg benzoin methyl ether, benzoin ether, rest) Propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl - Chloropridone and the like.

As the polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be suitably used. More specifically, for example, an amino acetophenone-based initiator as described in JP-A-10-291969, and a sulfhydryl phosphine oxide-based initiator described in Japanese Patent No. 42258899 can be used. .

As a hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade name: all manufactured by BASF). As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Corporation) which are commercially available products can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179, which has a wavelength of absorption of a long-wavelength source such as 365 nm or 405 nm, can be used. Further, as the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name: all manufactured by BASF Corporation) which is a commercially available product can be used.

As the polymerization initiator, a quinone compound is also preferably exemplified. As a specific example of the oxime-based initiator, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and JP-A-2006-342166 can be used. The compound described.

As the hydrazine compound such as an anthracene derivative which can be suitably used as a polymerization initiator in the present invention, for example, 3-benzylideneoxyimidobutan-2-one and 3-ethyloxyimino group can be mentioned. Butan-2-one, 3-propenyloxyimidobutan-2-one, 2-ethyloxyiminopentan-3-one, 2-ethyloxyimino-1- -Phenylpropan-1-one, 2-benzylideneoxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

As the oxime ester compound, for example, "British Chemical Society, JC Perkin II" (1979) pp. 1653-1660, Purkin's Journal II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, day The compound described in the publications of JP-A-2000-66385, JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166 Compounds, etc. Commercially available products such as IRGACURE-OXE01 (manufactured by BASF Corporation) and IRGACURE-OXE02 (manufactured by BASF Corporation) can be suitably used.

In addition, as the oxime ester compound other than the above, a compound described in Japanese Patent Laid-Open Publication No. 2009-519904, in which N is attached to the N-position of the carbazole, and a hetero substituent introduced into the diphenyl ketone moiety may be used. The compound described in the U.S. Patent No. 7,626,957, the compound described in Japanese Patent Laid-Open Publication No. 2010-15025, and the U.S. Patent Publication No. 2009-292039, the International Patent Publication No. 2009-131189 The ketone-based compound described in the publication, the compound described in US Pat. No. 7,569,910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, has an absorption maximum at 405 nm and has good sensitivity to a g-ray source. A compound or the like described in Japanese Laid-Open Patent Publication No. 2009-221114.

The cyclic anthraquinone compound described in JP-A-2007-2320, and JP-A-2007-322744 is preferably used. Among the cyclic ruthenium compounds, the cyclic ruthenium compound which is condensed in the carbazole dye described in Japanese Patent Laid-Open Publication No. 2010-185072, and the like, has high light absorbing property. It is preferable from the viewpoint of high sensitivity.

In addition, a Japanese patent having an unsaturated bond at a specific part of the ruthenium compound The compound described in JP-A-2009-242469 can achieve high sensitivity by regenerating active radicals from a polymerization inert radical, and can also be suitably used.

The ruthenium compound having a specific substituent as shown in JP-A-2007-269779 or the ruthenium compound having a thioaryl group as shown in JP-A-2009-191061 is exemplified.

Specifically, as the oxime polymerization initiator, a compound represented by the following formula (OX-1) is preferred. Further, the N-O bond of ruthenium may be a ruthenium compound of the (E) form, a ruthenium compound of the (Z) form, or a mixture of the (E) form and the (Z) form.

(In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.) In the above formula (OX-1), as represented by R The monovalent substituent is preferably a monovalent non-metal atomic group.

The monovalent non-metal atomic group may, for example, be an alkyl group, an aryl group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group or an arylthiocarbonyl group. Further, these groups may have one or more substituents. Further, the above substituent may be further substituted with another substituent.

The substituent may, for example, be a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a decyloxy group, a decyl group, an alkyl group or an aryl group.

The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, and a decyl group. Diyl, octadecyl, isopropyl, isobutyl, t-butyl, tert-butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, Benzomethazine methyl, 1-naphthylmethylmethyl, 2-naphthylmethylmethyl, 4-methylsulfonylbenzhydrylmethyl, 4-phenylsulfonylbenzimidylmethyl, 4-dimethylaminobenzimidylmethyl, 4-cyanobenzhydrylmethyl, 4-methylbenzimidylmethyl, 2-methylbenzimidylmethyl, 3-fluorobenzhydrylmethyl , 3-trifluoromethylbenzimidazole methyl, and 3-nitrobenzimidylmethyl.

The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and specific examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 9-fluorenyl group. , 9-phenanthryl, 1-fluorenyl, 5-fused tetraphenyl, 1-indenyl, 2-azulene, 9-fluorenyl, triphenyl, biphenyl, o-tolyl, M-tolyl, p-tolyl, xylyl, o- cumyl, m-isopropylphenyl and p-cumyl, 2,4,6-trimethyls, and cyclopentadienyl ( Pentalenyl), binaphthyl, binaphthyl, tetratetraphthyl, heptalenyl, biphenyl, indacenyl, propylene Fluorhenenyl, fluorenyl, vinyl fluorenyl, phenalenyl, fluorenyl, fluorenyl, hydrazino, hydrazinyl, hydrazino, fluorenyl, phenanthryl, sanya Phenyl, fluorenyl, fluorenyl, fused tetraphenyl, pleiadenyl, fluorenyl, fluorenyl, pentaphenyl, pentacenyl, tetraphenyl, hexaphenyl, hexa Phenyl, ruthenyl, fluorenyl, extended trinaphthyl (trinaphthylenyl), heptaphenyl, hexaphenyl, fluorenyl, and fluorenyl.

The fluorenyl group which may have a substituent is preferably a fluorenyl group having 2 to 20 carbon atoms, and specific examples thereof include an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, a trifluoroethyl fluorenyl group, a pentamidine group, and a benzene group. Formamyl, 1-naphthylmethyl, 2-naphthylmethyl, 4-methylsulfonylbenzimidyl, 4-phenylsulfonylbenzimidyl, 4-dimethylaminobenzamide Sulfhydryl, 4-diethylaminobenzhydryl, 2-chlorobenzhydryl, 2-methylbenzhydryl, 2-methoxybenzimidyl, 2-butoxybenzimidyl , 3-chlorobenzhydryl, 3-trifluoromethylbenzhydryl, 3-cyanobenzylidene, 3-nitrobenzhydryl, 4-fluorobenzhydryl, 4-cyano Benzopyridinyl, and 4-methoxybenzimidyl.

The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxy group. Alkylcarbonyl, hexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, octadecyloxycarbonyl, and trifluoromethoxycarbonyl.

Specific examples of the aryloxycarbonyl group which may have a substituent include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfonylphenoxycarbonyl group, and 4 -phenylsulfonylphenoxycarbonyl, 4-dimethylaminophenoxycarbonyl, 4-diethylaminophenoxycarbonyl, 2-chlorophenoxycarbonyl, 2-methylphenoxycarbonyl, 2-methoxyphenoxycarbonyl, 2-butoxyphenoxycarbonyl, 3-chlorophenoxycarbonyl, 3-trifluoromethylphenoxycarbonyl, 3-cyanophenoxycarbonyl, 3- Nitrophenoxycarbonyl, 4-fluorophenoxycarbonyl, 4-cyanophenoxycarbonyl, and 4-methoxyphenoxycarbonyl.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.

Specifically, a thienyl group, a benzo[b]thienyl group, a naphtho[2,3-b]thienyl group (naphtho[2,3-b] can be exemplified. Thienyl group), thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthene group (xanthenyl group), phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group (xanthenyl group) Pyridyl group), pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-mercapto group ( 3H-indolyl group), indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolizinyl group, isoquinolyl group Isoquinolyl group), quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl gr Oup), quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β- Β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, Phenasarazinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group (isoxazolyl group), furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group (pyrrolidinyl group), pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidinyl group (piperidyl group), piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and Thioxantolyl group.

As the alkylthiocarbonyl group which may have a substituent, specifically, a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, a octylthiocarbonyl group, a sulfonylthiocarbonyl group, and an eighteenth An alkylthiocarbonyl group, and a trifluoromethylthiocarbonyl group.

Specific examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl, 2-naphthylthiocarbonyl, 4-methylsulfonylphenylthiocarbonyl, and 4-phenylsulfonylsulfonate. Phenylthiocarbonyl, 4-dimethylaminophenylthiocarbonyl, 4-diethylaminophenylthiocarbonyl, 2-chlorophenylthiocarbonyl, 2-methylphenylthiocarbonyl, 2-methoxy Phenylthiocarbonyl, 2-butoxyphenylthiocarbonyl, 3-chlorophenylthiocarbonyl, 3-trifluoromethylphenylthiocarbonyl, 3-cyanophenylthiocarbonyl, 3-nitrophenylthio A carbonyl group, a 4-fluorophenylthiocarbonyl group, a 4-cyanophenylthiocarbonyl group, and a 4-methoxyphenylthiocarbonyl group.

In the above formula (OX-1), the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. Further, these groups may have one or more substituents. The substituent may be exemplified as the substituent. In addition, The above substituents may be further substituted by other substituents.

Among them, the structure shown below is particularly preferable.

In the following structures, the meanings of Y, X, and n are the same as Y, X, and n in the formula (OX-2) to be described later, and preferred examples are also the same.

In the above formula (OX-1), examples of the divalent organic group represented by A include an alkylene group having a carbon number of 1 to 12, a cycloalkylene group, and an alkynylene group. Further, these groups may have one or more substituents. The substituent may be exemplified as the substituent. Further, the above substituent may be further substituted with another substituent.

Among them, as A in the formula (OX-1), an unsubstituted alkylene group or an alkyl group (for example, a methyl group) is preferred from the viewpoint of improving sensitivity and suppressing coloration caused by heating over time. , ethyl, tert-butyl, dodecyl) substituted alkyl, alkenyl (eg vinyl, allyl) substituted alkyl, aryl (eg phenyl, p-tolyl, A tolyl, cumyl, naphthyl, anthracenyl, phenanthryl, styryl) substituted alkylene group.

In the above formula (OX-1), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent. As the substituent, the examples exemplified for the introduction into the aryl group which may have a substituent may be exemplified. The substituents in the aryl group are the same.

Among them, a substituted or unsubstituted phenyl group is preferred from the viewpoint of improving sensitivity and suppressing coloring caused by heating.

In the formula (OX-1), from the viewpoint of sensitivity, it is preferable that the structure of "SAr" formed by Ar in the above formula (OX-1) and S adjacent to Ar is as follows. structure. Further, Me represents a methyl group, and Et represents an ethyl group.

The hydrazine compound is preferably a compound represented by the following formula (OX-2).

[Chem. 26]

(In the formula (OX-2), R and X each independently represent a monovalent substituent, and A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5) The meanings of R, A, and Ar in OX-2) are the same as those of R, A, and Ar in the above formula (OX-1), and preferred examples are also the same.

In the above formula (OX-2), examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a decyloxy group, a decyl group, and an alkoxycarbonyl group. Amine group, heterocyclic group, halogen atom. Further, these groups may have one or more substituents. The substituent may be exemplified as the substituent. Further, the above substituent may be further substituted with another substituent.

Among these, X in the formula (OX-2) is preferably an alkyl group from the viewpoint of improving solvent solubility and absorption efficiency in a long wavelength region.

Further, n in the formula (2) represents an integer of 0 to 5, preferably an integer of 0 to 2.

In the above formula (OX-2), examples of the divalent organic group represented by Y include the structures shown below. In addition, in the base shown below, " ^* " represents the bonding position of Y and the adjacent carbon atom in the above formula (OX-2).

[化27]

Among them, from the viewpoint of high sensitivity, the structure shown below is preferable.

Further, the ruthenium compound is preferably a compound represented by the following formula (OX-3).

[化29]

(In the formula (OX-3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5) (OX-3) The meanings of R, X, A, Ar, and n are the same as those of R, X, A, Ar, and n in the above formula (OX-2), and preferred examples are also the same.

Specific examples (C-4) to specific examples (C-13) of the ruthenium compound which can be suitably used are shown below, but the present invention is not limited to these specific examples.

[化30]

The ruthenium compound has a maximum absorption wavelength in the wavelength range of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength range of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 455 nm. Compound.

From the viewpoint of sensitivity, the molar absorption coefficient of the cerium compound at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, particularly preferably from 5,000 to 200,000.

The molar absorption coefficient of the compound can be determined by a known method, specifically For example, it is preferably measured by a UV-visible spectrophotometer (Carry-5 spctrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.

The polymerization initiator to be used in the invention may be used in combination of two or more kinds as needed.

The polymerization initiator used in the composition of the present invention is preferably selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, and an α-hydroxyketone compound from the viewpoint of exposure sensitivity. , α-amino ketone compound, mercaptophosphine compound, phosphine oxide compound, metallocene compound, hydrazine compound, triallyl imidazole dimer, hydrazine compound, benzothiazole compound, diphenyl ketone compound, acetophenone A compound of the group consisting of a compound and a derivative thereof, a cyclopentadiene-benzene-iron complex compound and a salt thereof, a halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin compound.

More preferably, it is a trihalomethyltriazine compound, an α-amino ketone compound, a mercaptophosphine compound, a phosphine oxide compound, an anthraquinone compound, a triallyl imidazole dimer, an anthraquinone compound, a diphenylketone compound, or a phenylethyl group. The ketone compound is preferably at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-amino ketone compound, an anthraquinone compound, a triallyl imidazole dimer, and a diphenyl ketone compound. .

The content of the polymerization initiator contained in the composition of the present invention (the total content in the case of two or more kinds) is preferably 0.1% by mass or more and 50% by mass or less, more preferably, based on the total solid content of the composition. It is 0.5% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 20% by mass or less. Within this range, good sensitivity and pattern formation properties can be obtained.

<UV absorber>

The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, a salicylate-based, diphenylketone-based, benzotriazole-based, substituted acrylonitrile-based or triazine-based ultraviolet absorber can be used.

Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like, and a diphenyl ketone-based ultraviolet absorber. Examples thereof include 2,2'-dihydroxy-4-methoxydiphenyl ketone, 2,2'-dihydroxy-4,4'-dimethoxydiphenyl ketone, 2,2', 4,4'-tetrahydroxydiphenyl ketone, 2-hydroxy-4-methoxydiphenyl ketone, 2,4-dihydroxydiphenyl ketone, 2-hydroxy-4-octyloxydiphenyl ketone Wait. Further, examples of the benzotriazole-based ultraviolet absorber include 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, and 2 -(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-third amyl-5' -isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-butyl Phenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetra Methyl)phenyl]benzotriazole and the like.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate and 2-cyano-3,3-diphenylacrylate-2-ethylhexyl ester. Wait. Further, examples of the triazine-based ultraviolet absorber include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6. - bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2- Hydroxybenzene 4-[6,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis (2, Mono(hydroxyphenyl)triazine compound such as 4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-( 2,4-Dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-A Phenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl a bis(hydroxyphenyl)triazine compound such as-1,3,5-triazine; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxy Phenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6- A tris(hydroxyphenyl)triazine compound such as tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine.

The composition of the present invention is preferably used as a UV absorber as a compound represented by the following formula (I) as a conjugated diene compound.

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having a carbon number of 1 to 20 carbon atoms or an aryl group having 6 to 20, R & lt another ¹ and R ² may The same or different, but not the hydrogen atom at the same time.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, a propyl group, a n-butyl group, a n-hexyl group, a cyclohexyl group, a n-decyl group, and a n-dodecyl group. N-octadecyl, eicosyl, methoxyethyl, ethoxypropyl, 2-ethylhexyl, hydroxyethyl, chloropropyl, N,N-diethylaminopropyl, cyanoethyl , phenethyl, benzyl, p-tert-butylphenethyl, p-t-octylphenoxyethyl, 3-(2,4-di-p-pentylphenoxy)propyl, ethoxy A carbonylcarbonyl group, a 2-(2-hydroxyethoxy)ethyl group, a 2-furylethyl group or the like is preferably a methyl group, an ethyl group, a propyl group, a n-butyl group or a n-hexyl group.

The alkyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent of the alkyl group having a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a decyloxy group, and a halogen atom. , mercaptoamine, mercapto, alkylthio, arylthio, hydroxy, cyano, alkoxycarbonyl, aryloxycarbonyl, substituted aminecarboxamidine, substituted amine sulfonyl, nitro, substituted amine , alkylsulfonyl, arylsulfonyl and the like.

The aryl group having 6 to 20 carbon atoms represented by R ¹ and R ² may be a single ring or a condensed ring, and may be any of a substituted aryl group having a substituent or an unsubstituted aryl group. . For example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group, an acenaphthenyl group, a fluorenyl group, etc. are mentioned. Examples of the substituent of the substituted aryl group having a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a decyloxy group, a halogen atom, a decylamino group, a decyl group, an alkylthio group, and an aromatic group. A thio group, a hydroxy group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a substituted aminemethanyl group, a substituted amine sulfonyl group, a nitro group, a substituted amine group, an alkylsulfonyl group, an arylsulfonyl group or the like. Among them, a substituted or unsubstituted phenyl group, a 1-naphthyl group or a 2-naphthyl group is preferred.

Further, R ¹ and R ² may form a cyclic amine group together with a nitrogen atom. Examples of the cyclic amino group include a piperidinyl group, a morpholinyl group, a pyrrolidinyl group, a hexahydroazahetero group, and a piperazinyl group.

Among the above, R ¹ and R ^{2 are} preferably a lower alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, isopropyl group, butyl group, second butyl group, and third butyl group). Pentyl, third amyl, hexyl, octyl, 2-ethylhexyl, trioctyl, etc.), or substituted or unsubstituted phenyl (eg tolyl, phenyl, anisyl, 2,4,6-trityl, chlorophenyl, 2,4-di-t-pentylphenyl, etc.). Further, it is also preferred that R ¹ and R ^{2 are} bonded to each other and a nitrogen atom represented by N in the formula is formed to form a ring (e.g., a piperidine ring, a pyrrolidine ring, a morpholine ring, etc.).

In the above formula (I), R ³ and R ⁴ represent an electron withdrawing group. Here, the electron withdrawing group is a zeta electron value of a substituent constant σ _p value (hereinafter, abbreviated as "σ _p value") of Hammett is 0.20 or more and 1.0 or less. Preferably, the σ _p value is 0.30 or more and 0.8 or less.

The Hammett's rule is to quantitatively discuss the effects of substituents on the reaction or balance of benzene derivatives, and the rule of thumb advocated by Hammett in 1935 is widely recognized today. Sex. The substituent constants obtained by Hammett's law have σ _p values and σ _m values, which are described in many common books. For example, see "Dan's Handbook of Chemistry" by Dean. (Lange's Handbook of Chemistry)" 12th Edition, 1979 (McGraw-Hill) or "Chemical Supplement", 122, 96-103 pages, 1979 (Nanjiang Hall), "Chemistry Chemical Reviews, 91, 165-195, 1991. In the present invention, it is not meant to be limited only to the substituents having the values known from the documents described in the books, even if the value is unknown to the literature, as long as it is included in the measurement according to the Hammett's law. Within the scope, the substituent is of course also included.

Specific examples of the electron withdrawing group having a σ _p value of 0.20 or more and 1.0 or less include an anthracenyl group, a decyloxy group, an amine carbaryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, and a nitro group. Dialkylphosphonium, diarylphosphonium, diarylphosphinyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfonium oxide a thiol group, an anthracene group, an sulfonyl group, a thiocyanate group, a thiocarbonyl group, an alkyl group substituted with at least two or more halogen atoms, an alkoxy group substituted with at least two or more halogen atoms, and at least 2 One or more halogen atom-substituted aryloxy groups, an alkylamino group substituted with at least two or more halogen atoms, an alkylthio group substituted with at least two or more halogen atoms, and other pulls having a σ _p value of 0.20 or more An electron-substituted aryl group, a heterocyclic group, a chlorine atom, a bromine atom, an azo group, or a selenocyanate group. Among the substituents, the group which may further have a substituent may further have a substituent as exemplified above.

Among the above, in the present invention, R ^{3 is} preferably a group selected from the group consisting of a cyano group, -COOR ⁵ , -CONHR ⁵ , -COR ⁵ , and -SO ₂ R ⁵ , and further preferably R ⁴ . It is a group selected from the group consisting of a cyano group, -COOR ⁶ , -CONHR ⁶ , -COR ⁶ , and -SO ₂ R ⁶ .

R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The meaning of the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by R ⁵ and R ⁶ is the same as in the case of the above R ¹ and R ² , and the preferred embodiment is also the same. .

Among these, as R ³ and R ⁴ , a mercapto group, an amine mercapto group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group or an arylsulfonyl group is preferred. , sulfonyloxy, sulfonyl, especially preferably fluorenyl, amine carbyl, alkoxycarbonyl, aryloxycarbonyl, cyano, alkylsulfonyl, arylsulfonyl, sulfonium oxide Base, amine sulfonyl.

Further, R ³ and R ⁴ may be bonded to each other to form a ring.

Further, it may be in the form of a polymer derived from a monomer in which at least one of R ¹ , R ² , R ³ and R ⁴ is bonded to a vinyl group via a linking group. It may also be a copolymer with other monomers. In the case of a copolymer, as other monomers, there are acrylic acid, α-chloroacrylic acid, and α-alkylacrylic acid (for example, an ester derived from an acrylic acid such as methacrylic acid, preferably a lower alkyl ester and a decylamine, For example, acrylamide, methacrylamide, butyl butyl decylamine, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, acrylic acid 2-ethylhexyl ester, n-hexyl acrylate, octyl methacrylate, and lauryl methacrylate, methylene bis acrylamide, etc., vinyl esters (such as vinyl acetate, vinyl propionate and vinyl laurate) Ester, etc.), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (such as styrene and its derivatives, such as vinyl toluene, divinylbenzene, vinyl acetophenone, sulfonated styrene, and styrene Sulfonic acid, etc., itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (such as vinyl ether, etc.), maleic acid ester, N-vinyl-2-pyrrole Pyridone, N-vinylpyridine, 2-vinylpyridine and 4-vinyl Pyridine and so on.

Among them, particularly preferred are acrylates, methacrylates, and aromatic vinyl compounds.

Two or more kinds of the above comonomer compounds may be used in combination. For example, n-butyl acrylate and divinyl benzene, styrene and methyl methacrylate, C can be used. Methyl enoate and methacrylate, and the like.

Hereinafter, preferred specific examples of the compound represented by the above formula (I) [exemplary compound (1) to exemplary compound (14)] are shown. However, in the present invention, it is not limited by these specific examples.

[化34]

The compound represented by the general formula (I) in the present invention can be exemplified by the Japanese Patent Publication No. Sho 44-29620, the Japanese Patent Laid-Open No. Hei 53-128333, the Japanese Patent Laid-Open No. 61-169831, and the Japanese Patent. It is synthesized by the method described in JP-A-63-53543, JP-A-63-53544, and JP-A-63-56651.

The commercially available product is, for example, a diethylamino-phenylsulfonyl-pentadienoic acid-based ultraviolet absorber (manufactured by FUJIFILM Fine Chemicals, trade name: DPO). In the present invention, the above various ultraviolet absorbers may be used alone or in combination of two or more.

When the ultraviolet absorber is contained in the radiation-sensitive linear composition of the present invention, the content of the ultraviolet absorber is preferably 0.01% by mass to 30% by mass based on the total solid content of the composition. Preferably, it is 0.01% by mass to 20% by mass, particularly preferably 0.01% by mass to 15% by mass, most preferably 3% by mass to 10% by mass. When the content of the ultraviolet absorber is 0.01% by mass or more, the light shielding ability at the time of exposure is good, and the pattern line width is prevented from being coarsened due to excessive polymerization, whereby a desired line width can be easily obtained, and the periphery can be further suppressed. Production of residue (developing residue). In addition, when it is 30% by mass or less, light shielding at the time of exposure The ability is not too strong and the aggregation proceeds better.

<solvent>

The radiation sensitive composition of the present invention can generally be constructed using a solvent (usually an organic solvent).

The solvent is not particularly limited as long as it satisfies the solubility of each component or the coating property of the radiation-sensitive composition, but is preferably selected in consideration of solubility, coating property, and safety of the ultraviolet absorber and the binder. Further, when the radiation sensitive composition of the present invention is prepared, it is preferred to contain at least two kinds of solvents.

As the solvent, preferred are esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, Ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl glycolate, ethyl hydroxyacetate, butyl glycolate, methyl methoxyacetate, methoxyacetic acid Ester, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.; alkyl 3-hydroxypropionate such as methyl 3-hydroxypropionate or ethyl 3-hydroxypropionate, For example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.; methyl 2-hydroxypropionate, 2-hydroxypropionic acid alkyl esters such as ethyl 2-hydroxypropionate and propyl 2-hydroxypropionate, for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methyl Propyl oxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropanoate, 2-oxy-2-methyl Ethyl propionate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, etc.; methyl pyruvate, ethyl pyruvate Pyruvate, propyl pyruvate, methyl acetyl, acetyl ethyl acetate, 2-oxobutanoate, Ethyl 2-oxobutanoate, etc.; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve Acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol single A propyl ether acetate or the like; a ketone such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone or the like; an aromatic hydrocarbon such as toluene or xylene.

As described above, in view of the solubility of the ultraviolet absorber and the alkali-soluble resin, and the improvement of the coating surface, two or more kinds of the above solvents may be mixed, and in particular, the following mixed solution may be suitably used. Selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methyl Two or more of methyl oxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate .

The content of the solvent in the radiation sensitive composition is preferably such that the total solid content concentration of the composition becomes 5 mass% to 90 mass%, more preferably 5 mass% to 87%. The amount of mass % is particularly preferably from 10% by mass to 85% by mass, and more preferably from 50% by mass to 85% by mass.

<Close Agent>

In order to improve the adhesion between the layers or the adhesion between the photosensitive layer and the substrate, a known so-called adhesion improver can be used for each layer.

For example, the adhesion improving agent described in Japanese Patent Laid-Open Publication No. Hei No. Hei 5- No. Hei. Specific examples thereof include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinylmethyl- 1-phenyl-triazole-2-thione, 3-morpholinylmethyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinylmethyl-thiazide Oxazole-2-thione, and 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, benzotriazole containing amine group, decane Mixture, etc.

As the adhesion improving agent, a decane coupling agent is preferred.

The decane coupling agent preferably has an alkoxyalkyl group as a hydrolyzable group capable of chemically bonding with an inorganic material. Further, it is preferred to have a group which exhibits affinity with an organic resin to form an bond or form a bond, and preferably has a (meth)acryl fluorenyl group, a phenyl group, a fluorenyl group, a glycidyl group or an oxetane. As the base, oxetanyl is preferred among those having a (meth) acrylonitrile group or a glycidyl group.

In other words, the decane coupling agent used in the present invention is preferably a compound having an alkoxyalkyl group, a (meth) acryl fluorenyl group or an epoxy group, and specifically, a methyl group having the following structure An acryloyl-trimethoxydecane compound, a glycidyl-trimethoxydecane compound, and the like.

[化35]

Further, the decane coupling agent in the present invention is preferably a decane compound having at least two functional groups having different reactivity in one molecule, and particularly preferably an amine group and an alkoxy group as a functional group. As such a decane coupling agent, for example, N-β-aminoethyl-γ-aminopropyl-methyldimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-602), N- β-Aminoethyl-γ-aminopropyl-trimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-603), N-β-aminoethyl-γ-aminopropyl-tri Ethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-602), γ-aminopropyl-trimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-903), γ-aminopropyl Base-triethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-903), 3-methacryloxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) Wait.

The content of the adhesion improving agent is preferably 0.001% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass, particularly preferably 0.1% by mass, based on all components other than the solvent of the composition of the present invention. 5 mass%.

<Polymerization inhibitor>

In the composition of the present invention, in order to prevent unwanted thermal polymerization of the polymerizable compound during or during the production of the composition, it is desirable to add Add a small amount of polymerization inhibitor.

Examples of the polymerization inhibitor which can be used in the present invention include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, and benzene.醌, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N - nitrosophenylhydroxylamine trivalent phosphonium salt and the like.

The amount of the polymerization inhibitor added is preferably from 0.005% by mass to 5% by mass, and more preferably from 0.01% by mass to 5% by mass, based on the mass of the entire composition.

<Surfactant>

In the composition of the present invention, various surfactants may be added from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used.

In particular, the composition of the present invention further improves liquid characteristics (particularly fluidity) when it is prepared as a coating liquid by containing a fluorine-based surfactant, so that uniformity of coating thickness or liquid-saving property can be further improved.

In other words, when a film is formed using a coating liquid to which a composition containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is lowered, whereby the wettability to the surface to be coated is obtained. Improved, and the applicability to the coated surface is improved. Therefore, even when a film having a thickness of about several μm is formed with a small amount of liquid, it is effective to form a film having a uniform thickness with a small thickness unevenness.

The fluorine content in the fluorine-based surfactant is suitably 3% to 40%. The amount % is more preferably 5% by mass to 30% by mass, particularly preferably 7% by mass to 25% by mass. Fluorine content rate The fluorine-based surfactant in this range is effective from the viewpoint of the uniformity of the thickness of the coating film or the liquid-saving property, and the solubility in the composition is also good.

Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, and Megafac F479. Megafac F482, Megafac F554, Megafac F780, Megafac F781 (above, manufactured by Di Aisheng (DIC)), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above, Sumitomo 3M (share)), Surflon S -382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above, Asahi Glass (share) Manufactured), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA).

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, Glycerol ethoxylate, etc., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol Dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704 manufactured by BASF Corporation) , 901, 904, 150R1), Solsperse 20000 (Lubrizol, Japan) () manufacturing) and so on.

Specific examples of the cation-based surfactant include an anthraquinone derivative (trade name: EFKA-745, manufactured by Morishita Industry Co., Ltd.), and an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (meth)acrylic (co)polymer Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.).

Examples of the anthrone-based surfactant include Toray. "Toray Silicone DC3PA", "Toray Silicone SH7PA", "Toray Silicone SH11PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Toray Silicone SH30PA", "Toray" manufactured by Dow Corning (share) Silicone SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF-4452" manufactured by Momentive Performance Materials, Shin-Etsu "KP341", "KF6001", "KF6002" manufactured by Shinetsu Silicon Co., Ltd., "BYK307", "BYK323", "BYK330" manufactured by BYK Chemie.

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

The amount of the surfactant added is preferably from 0.001% by mass to 2.0% by mass, and more preferably from 0.005% by mass to 1.0% by mass based on the total mass of the composition.

<Other Additives>

In the radiation sensitive composition of the present invention, various kinds of additions can be adjusted as needed. Additives such as a polymerization inhibitor, a surfactant, a filler, a polymer compound other than the above, an antioxidant, an anti-agglomerating agent, and the like.

Specific examples of the additives include fillers such as glass and alumina; 2,2-thiobis(4-methyl-6-tert-butylphenol) and 2,6-di-third. An antioxidant such as butyl phenol; and an anti-agglomerating agent such as sodium polyacrylate.

In addition, when the alkali solubility of the ultraviolet non-irradiated portion of the radiation sensitive composition is promoted and the developability is further improved, the radiation sensitive composition of the present invention may contain an organic carboxylic acid, preferably having a molecular weight of 1,000 or less. Low molecular weight organic carboxylic acid.

Specific examples of the organic carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, diethylacetic acid, heptanoic acid, and caprylic acid; oxalic acid; Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid, methylmalonic acid, ethylmalonic acid, Aliphatic dicarboxylic acid such as dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid, citraconic acid; 1,2,3-propane tricarboxylic acid (tricarballylic acid), ornithine An aliphatic tricarboxylic acid such as a camphoric acid; an aromatic one such as benzoic acid, toluic acid, 4-isopropylbenzoic acid, 2,3-dimethylbenzoic acid or 3,5-dimethylbenzoic acid Carboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid, trimesic acid, 1,2,3,5-benzenetetracarboxylic acid, 1,2,4 , an aromatic polycarboxylic acid such as 5-benzenetetracarboxylic acid; phenylacetic acid, hydrogen ato acid, hydrogen cinnamic acid, mandelic acid, phenyl succinic acid, atopic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid Benzyl ester, cinnamylidene acetic acid, Beans, umbellic acid (umbellic acid), and other carboxylic acid.

Further, the radiation sensitive composition of the present invention may contain a trace amount of a coloring agent (a known dye, a pigment, etc. (including black such as carbon black or titanium black) as long as it is a range of a white (transparent) pattern in which a solid-state imaging element can be formed. Agent)), but preferably free of colorants.

Specifically, from the viewpoint of the transmittance of the transparent pattern, the content of the coloring agent in the total solid content of the radiation sensitive composition is preferably 3.0% by mass or less, more preferably 1.0% by mass or less, and particularly preferably 0%. % by mass (ie, no colorant form).

The radiation sensitive composition of the present invention described above can be preferably used for the formation of a transparent material, particularly a pixel of a solid-state imaging element (particularly, a transparent pixel as a transparent pattern).

From the viewpoint of being suitable for such use, the radiation sensitive composition of the present invention preferably has a transmittance in all regions of a wavelength region of 400 nm to 700 nm when a film having a film thickness of 1 μm is formed. More than 90% (more preferably 95% or more).

<Filter Filtering>

In order to remove foreign matter or reduce defects and the like, it is preferred to filter the composition of the present invention with a filter. It is not particularly limited as long as it is a filter used for filtration purposes or the like from the past.

The filter used for the filter filtration can be used without particular limitation as long as it is a filter for filtration use or the like.

Examples of the material of the filter include fluororesins such as polytetrafluoroethylene (PTFE); nylon-6, nylon-6, 6, and the like. Polyamide resin; polyolefin resin (high density, ultrahigh molecular weight) such as polyethylene or polypropylene (PP). Among these raw materials, polypropylene (including high density polypropylene) is preferred.

The pore diameter of the filter is not particularly limited, and is, for example, about 0.01 μm to 20.0 μm, preferably about 0.01 μm to 5 μm, and more preferably about 0.01 μm to 2.0 μm.

By setting the pore diameter of the filter to the above range, fine particles can be removed more effectively, and turbidity can be further reduced.

Here, the pore size of the filter can be referred to the nominal value of the filter manufacturer. As a commercially available filter, for example, from Japan Pall Co., Ltd., Advantec Toyo Co., Ltd., Japan Nihon Entegris Co., Ltd. (formerly Japan Mico) Choose from various filters provided by Mykrolis Co., Ltd. or Kitz Microfilter Co., Ltd.

In the above filter filtration, two or more types of filters may be used in combination.

For example, the first type of filter may be used for the first filtration, and the second type of filter having a different pore size than the first type of filter may be used for the filtration.

In this case, the filtration by the first filter and the filtration by the second filter may be performed only once or twice or more.

As the second filter, a filter formed of the same material as that of the above-described first filter can be used.

The radiation sensitive composition of the present invention can be hardened and is preferably used as various A cured film of a component or the like. Specifically, a coloring layer of a color filter can be cited.

Examples of the element including the color filter of the present invention include a solid-state imaging device (for example, a CMOS image sensor, an organic CMOS image sensor), a liquid crystal display device, and an organic EL display device.

The method for producing a cured film of the present invention is disclosed as a method for producing a cured film, which is characterized by comprising: (1) a step of applying the radiation-sensitive composition of the present invention to a substrate; (2) a step of exposing the applied radiation-sensitive composition; and (3) a step of developing the exposed radiation-sensitive composition; and (4) performing the developed radiation-sensitive composition A post-baking step of heat hardening.

"Color filter and its manufacturing method"

The method for producing a color filter of the present invention comprises: (1) a step of applying the radiation sensitive composition of the present invention to a substrate (film formation step); (2) exposing the applied radiation sensitive composition a step of exposing (exposure step); (3) a step of developing the exposed radiation-sensitive composition; and (4) a post-baking step of thermally curing the developed radiation-sensitive composition (developing step) . Further, a step of hardening the film or the pattern by heating and exposure may be included as needed.

Further, the color filter of the present invention is a color filter obtained by the above-described manufacturing method.

In the method of manufacturing the color filter of the present invention, the use of the analytic property is excellent Since the radiation sensitive composition of the present invention which suppresses the deterioration of the rectangularity of the pattern in the post-baking in the subsequent step, the pixel (excellent) of the pixel (pattern) can be obtained, and fine and high-quality images can be obtained. Display color filters.

The term "color" in the color filter of the present invention means a "color" in a broad sense, and includes a concept of achromatic color such as transparency in addition to chromatic colors such as red, blue, and green. That is, the pattern of the color filter of the present invention may be a colored pattern such as red, blue, or green, or may be an achromatic pattern such as transparent.

In addition, the color filter of the present invention may be formed by combining at least one of a colored pattern such as red, blue, and green, and at least one of a clear color such as a transparent pattern. As such an example, a color filter including a red pattern (red pixel), a blue pattern (blue pixel), a green pattern (green pixel), and a transparent pattern (transparent pixel) can be cited.

Further, in the present invention, the term "transparent pattern" means a pattern showing high transmittance in all areas of visible light, and preferably in a wavelength region of 400 nm to 700 nm when the film thickness is 1 μm. The transmittance of the region is 90% or more (more preferably 95% or more).

Hereinafter, a method of forming a transparent pattern in a color filter for an image sensor will be described as an example of a method of manufacturing a color filter of the present invention.

As the substrate, it is preferable to use a germanium wafer or to provide another layer on the germanium wafer.

As a method of applying the radiation-sensitive composition, coating is preferred, and various methods such as a spray method, a roll coating method, and a spin coating method can be used.

The exposure is a step of performing pattern exposure by irradiating light (preferably ultraviolet light) through a photomask.

The ultraviolet rays used for at least the above exposure are preferably at least one of g-rays, h-rays, and i-rays, and more preferably i-rays.

As the exposure machine, for example, a stepper can be suitably used.

Development is carried out by developing the exposed film with an alkaline developing solution.

As the alkaline developing solution, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; and diethylamine can be used. a secondary amine such as di-n-propylamine; a tertiary amine such as trimethylamine, methyldiethylamine, dimethylethylamine or triethylamine; an alkyl alcohol such as dimethylethanolamine, methyldiethanolamine or triethanolamine. Amines; pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo [4.3.0] cyclic tertiary amines such as 5-decene; aromatic tertiary amines such as pyridine, collidine, lutidine, quinoline; tetramethylammonium hydroxide An aqueous solution of a quaternary ammonium salt such as tetraethylammonium hydroxide.

Further, an appropriate amount of a water-soluble solvent such as methanol or ethanol and/or a surfactant may be added to the alkaline developing solution.

The development method may be any one of a puddle type development method, a dipping method, and a shower method, and the development time is usually 30 seconds to 180 seconds.

After the alkali development, for example, a running water rinse is performed for 30 seconds to 90 seconds, and then dried by, for example, compressed air or compressed nitrogen, thereby forming a pattern.

Then, after exposing the pattern after alkali development to ultraviolet light again, it is preferably heated at a predetermined temperature, for example, 150 ° C to 250 ° C for a predetermined period of time, for example, by heating using a heating means such as a hot plate or an oven. The plate is post-baked for 5 minutes to 30 minutes, and in the oven, post-baking is performed for 30 minutes to 90 minutes, whereby a predetermined transparent pattern can be formed.

The transparent pattern formed in the above manner has an arrangement of a plurality of rectangular pixels on the substrate, and one side (maximum side) of the pixel is usually 1.0 μm to 20 μm or less, and the substrate is efficiently used. From the viewpoint of miniaturization of the element using the solid-state imaging element and high-speed operation of the solid-state imaging element, it is preferably 5 μm or less, more preferably 4 μm or less, and particularly preferably 3 μm or less.

In addition, the thickness of the pixel in the color filter of the present invention is not particularly limited. However, in view of the effective use of a substrate such as a wafer, the shading of the element using the solid-state imaging element exists. The tendency to be thinned is preferably 2 μm or less, more preferably 1.5 μm or less, and particularly preferably 1.0 μm or less.

The color filter of the present invention can be used for a liquid crystal display device, a solid-state imaging device (for example, a CMOS sensor, an organic CMOS sensor), or an organic EL device, and is particularly suitable for solid-state photography applications. When used in a liquid crystal display device, a metal complex dye having excellent spectral characteristics and heat resistance is used as a colorant, and alignment defects of liquid crystal molecules with a decrease in specific resistance are small, and the color of a display image is good and display characteristics are excellent.

<Liquid crystal display device>

The color filter of the present invention is excellent in color tone and excellent in light resistance. Since it is a coloring element, it is particularly suitable as a color filter for a liquid crystal display device. A liquid crystal display device having such a color filter can display a high-quality image, and the display image of the high-quality image has good color and excellent display characteristics.

For the definition of the display device or the details of each display device, for example, "Electronic display elements (Kosyo Chosakai Publishing (shares) issued in 1990)" and "Display devices (Ibuki Shunzhang, The industrial book (Sangyo Tosho) (issued in 1989) is listed in the book. In addition, the liquid crystal display device is described in, for example, "Next-generation liquid crystal display technology (edited by Uchida Natsuo, Industrial Research Association (share), 1994). The liquid crystal display device to which the present invention is applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "next generation liquid crystal display technology".

Among them, the color filter of the present invention is particularly effective for a liquid crystal display device of a Thin Film Transistor (TFT) type. A color TFT liquid crystal display device is described in, for example, "Color TFT Liquid Crystal Display (Kyoritsu Publishing Co., Ltd., 1996)". Further, the present invention can also be applied to a liquid crystal whose viewing angle is expanded, such as a horizontal electric field driving method such as an in-line switching (IPS), or a pixel division method such as a multi-domain vertical alignment (MVA). Display device, or Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optical Circuit Switching (OCS), Fringe Electric Field Switching (Fringe Field Switching, FFS), and Reflective Optically Compensated Bend (Reflective Optically Compensated Bend, R-OCB) and so on.

In addition, the color filter of the present invention is also available in a bright and high-definition Color-filter On Array (COA) mode. In the COA liquid crystal display device, in addition to the usual required characteristics as described above, the required characteristics of the color filter layer may require characteristics for the interlayer insulating film, that is, low dielectric constant and peeling resistance. . In the color filter of the present invention, it is considered that the (A) metal complex dye and the (B) complex-forming compound of the present invention are cured in the above ratio, and are obtained. In order to extremely effectively prevent the decrease in the specific resistance of the liquid crystal material, the alignment hindrance of the liquid crystal molecules, that is, the deterioration of the display characteristics, is eliminated. Thereby, since the color purity and the like are excellent and the color is excellent, a COA liquid crystal display device having high resolution and excellent long-term durability can be provided. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

Further, in the coloring layer formed by the COA method, in order to electrically connect the indium tin oxide (ITO) electrode disposed on the colored layer and the terminal of the driving substrate below the colored layer, it is necessary to form one side. a rectangular through hole having a length of about 1 μm to 15 μm or a U-shaped concave guide channel, particularly preferably having a size of the guide channel (that is, a length of one side) of 5 μm or less, but by using the present invention It can also form a guide channel of 5 μm or less. For the image display methods, for example, "EL, PDP (plasma display panel), LCD (liquid crystal display device) display - technology and market trends - (Toray Research Center research and research department 2001) It is described on page 43 of the issue).

The liquid crystal display device of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle securing film, in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device including such well-known members. For example, "The market of the '94 liquid crystal display peripheral materials and chemicals (Island Kentaro CMC (share) issued in 1994), "2003 liquid crystal related market status and future prospects (volume) (Table Liangji Fuji It is described in the Fuji Chimera Research Institute (shares, issued in 2003).

For the backlight, SID meeting Digest 1380 (2005) (A. Konno et al.), or Monthly Display of the December 2005 issue of the 18th ~ It is recorded in the 24th page (Island Kang Yu), the 25th page of the December 2005 issue of the Display Monthly, and the 30th page (Yumu Longming).

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a three-wavelength tube of a conventionally known cold cathode tube, and further, by using red, green, and blue light-emitting diodes A (Light Emitting Diode, LED) light source (RGB-LED) is used as a backlight to provide a liquid crystal display device having high luminance, high color purity, and good color reproducibility.

<Solid photographic element>

The solid-state imaging device of the present invention includes the color filter for a solid-state imaging device of the present invention described above. The solid-state imaging device of the present invention has a configuration in which the color filter for a solid-state imaging device of the present invention is provided, as long as it is a solid-state imaging device. The configuration that functions is not particularly limited, and examples thereof include the following configurations.

In this configuration, a plurality of photodiodes (photodiodes) constituting a light receiving region of a solid-state imaging device (a charge coupled device (CCD) image sensor, a CMOS image sensor, etc.) are provided on the support, and A transfer electrode including a polycrystalline silicon or the like has a light-shielding film containing tungsten or the like which is opened only to the light-receiving portion of the photodiode, and has a light-shielding film covering the entire surface of the light-shielding film. And an element protective film containing tantalum nitride or the like formed by the photodiode light receiving portion, and the color filter for solid-state imaging device of the present invention is provided on the element protective film.

Furthermore, it is also possible to have a configuration such as a concentrating device (for example, a microlens or the like, the same applies hereinafter) on the element protective layer and under the color filter (on the side close to the support), or in color The filter has a configuration of a concentrating device.

In addition, it can also be a CMOS image sensor of an organic CMOS or Quantum Film.

- Organic CMOS (Organic Complementary Metal Oxide Semiconductor Image Sensor) -

The organic CMOS sensor includes a full-color photosensitive organic photoelectric conversion film as a film of a photoelectric conversion layer, and a CMOS signal readout substrate, and functions as an organic material for capturing light and converting the light into an electrical signal. A hybrid structure of a two-layer structure that assumes an action of taking an electric signal to the outside, in principle, makes the aperture ratio 100% with respect to the incident light. The organic photoelectric conversion film is a continuous film with a free structure and can be laid on a CMOS signal readout substrate, so that expensive micromachining is not required. Process, and suitable for micro-finishing.

An example of an imaging element as an organic CMOS will be described using a diagram.

FIG. 1 is a schematic cross-sectional view showing a configuration of a laminated imaging element (organic CMOS).

The imaging element 100 shown in FIG. 1 includes a substrate 101, an insulating layer 102, a connection electrode 103, a pixel electrode 104, a connection portion 105, a connection portion 106, an organic layer 107, a counter electrode 108, a buffer layer 109, and a sealing layer 110. The color filter 111, the partition wall 112, the light shielding layer 113, the protective layer 114, the counter electrode voltage supply unit 115, and the readout circuit 116.

By using the color filter of the present invention described above as the color filter 111, it is possible to obtain an image pickup element having low noise and good color reproducibility.

The substrate 101 is a glass substrate or a semiconductor substrate such as germanium. An insulating layer 102 is formed on the substrate 101. A plurality of pixel electrodes 104 and a plurality of connection electrodes 103 are formed on the surface of the insulating layer 102.

The organic layer 107 is composed of at least a photoelectric conversion layer. The photoelectric conversion layer is a layer that generates electric charges corresponding to the received light, and is a layer containing an inorganic or organic photoelectric conversion material. The organic layer 107 is provided by covering the pixel electrodes 104 on the plurality of pixel electrodes 104. The organic layer 107 has a thickness that is fixed to the pixel electrode 104, but is substantially trapezoidal at its end portion inclined toward the substrate 101 side.

Further, the organic layer 107 includes not only a layer composed of only an organic material but also a layer including a part of an inorganic material.

The counter electrode 108 is an electrode opposed to the pixel electrode 104, which is organic The layer 107 is covered with the organic layer 107 to be disposed. In order to inject light into the organic layer 107, the counter electrode 108 includes a conductive material (for example, ITO or the like) that is transparent with respect to the incident light. The counter electrode 108 is formed to be disposed on the connection electrode 103 outside the organic layer 107, and is electrically connected to the connection electrode 103.

The connection portion 106 is a plug or the like embedded in the insulating layer 102 to electrically connect the connection electrode 103 and the counter electrode voltage supply portion 115. The counter electrode voltage supply unit 115 is formed on the substrate 101, and a predetermined voltage is supplied to the counter electrode 108 via the connection unit 106 and the connection electrode 103. When the voltage to be supplied to the counter electrode 104 is higher than the power supply voltage of the imaging element 100, the voltage is boosted by a booster circuit such as a charge pump to generate the predetermined voltage.

The pixel electrode 104 is an electrode for trapping charges for trapping charges generated in the organic layer 107 between the pixel electrode 104 and the counter electrode 108 opposed thereto. The readout circuit 116 is disposed on the substrate 101 corresponding to each of the plurality of pixel electrodes 104, and reads out a signal corresponding to the electric charge captured by the corresponding pixel electrode 104. The readout circuit 116 includes, for example, a CCD, a metal oxide semiconductor circuit, a TFT circuit, or the like, and is shielded from light by a light shielding layer (not shown).

The buffer layer 109 is formed by covering the counter electrode 108 with the counter electrode 108. The sealing layer 110 is formed by covering the buffer layer 109 with the buffer layer 109. The color filter 111 is formed on the sealing layer 110 at a position opposed to each of the pixel electrodes 104. The partition walls 112 are disposed in the gaps between the color filters 111 to enhance the light transmission efficiency of the color filters 111. The light shielding layer 113 is formed on the sealing layer 110 In a region other than the region where the color filter 111 and the partition wall 112 are provided, light is prevented from entering the peripheral circuit. The protective layer 114 is formed on the color filter 111, the partition wall 112, and the light shielding layer 113 to protect the entire photographic element.

Further, in the example of FIG. 1, the pixel electrode 104 and the connection electrode 103 are embedded in the surface portion of the insulating layer 102, but the electrodes may be formed on the insulating layer 102. Further, two sets of the connection electrode 103, the connection portion 106, and the counter electrode voltage supply unit 115 are provided, but the combination may be one set. As in the example of FIG. 1, by supplying a voltage from the both end portions of the counter electrode 108 toward the counter electrode 108, the voltage drop in the counter electrode 108 can be suppressed. The number of the combinations may be appropriately increased or decreased in consideration of the wafer area of the element.

The photographing element 100 has a plurality of pixel parts. In a state in which the substrate 101 is viewed from the incident side of the light, the plurality of pixel portions are arranged in a two-dimensional shape. The pixel portion includes a pixel electrode 104, an organic layer 107, a counter electrode 108 opposed to the pixel electrode 104, a sealing layer 110, a color filter 111, a partition wall 112, and a readout circuit 116.

Next, a configuration example of the peripheral circuit will be described. The readout circuit 116 preferably uses a CCD circuit or a CMOS circuit in a general image sensor application. Further, in terms of noise and high speed, it is preferable to use a CMOS circuit. The configuration example of the peripheral circuit described below is an example of a configuration in which a CMOS circuit is used as the readout circuit 116.

FIG. 2 is a view showing an example of the overall configuration of a peripheral circuit including the imaging element shown in FIG. 1. As shown in FIG. 2, in the photographic element 100, in addition to the configuration shown in FIG. 1, a vertical driver (driver) 121 and a timing generator (timing) are included. A generator 122, a signal processing circuit 123, a horizontal driver 124, an LVDS (Low Voltage Differential Signaling) 125, a serial conversion unit 126, and a pad 127.

The pixel area shown in FIG. 2 corresponds to the first area R1 shown in FIG. 1. Each block within the pixel region represents the readout circuit 116. The peripheral circuit of the photographic element can be substantially the same as the peripheral circuit used in a general CMOS image sensor. The imaging element differs from the peripheral circuit configuration of a general CMOS image sensor in that a counter electrode voltage supply unit 115 is added.

The pad 127 is an interface for input and output with the outside. The timing generator 122 supplies timing for driving the imaging element, and performs readout control such as elongated interval reading or partial reading. The signal processing circuit 123 is provided corresponding to each column of the readout circuit 116. The signal processing circuit 123 performs Correlated Double Sampling (CDS) processing on the signals output from the corresponding columns, and converts the processed signals into digital signals. The signal processed by the signal processing circuit 123 is stored in a memory set in each column. The vertical driver 121 performs control of reading a signal from the readout circuit 116 and the like. The horizontal driver 124 sequentially reads out signals of one line stored in the memory of the signal processing circuit 123 and outputs them to the control in the LVDS 125. The LVDS 125 transmits a digital signal in accordance with LVDS (Low voltage differential signaling). The serial conversion unit 126 converts the input parallel digital signals into a series and outputs them.

Further, the serial conversion unit 126 may be omitted. In addition, in the signal processing circuit 123, it is assumed that only the correlated double sampling processing is performed, and the analog digital position can also be set. (Analog-to-Digital, AD) conversion circuit instead of the LVDS 125. Further, in the signal processing circuit 123, only the correlated double sampling processing is performed, and the LVDS 125 and the serial conversion unit 126 may be omitted. In this case, an AD conversion circuit may be provided outside the imaging element wafer. Further, the signal processing circuit 123, the LVDS 125, and the serial conversion unit 126 may be disposed on one of the regions adjacent to the pixel region and the other. In this case, a configuration may be adopted in which one of the columns of the readout circuit 116 (for example, an odd column) is processed by one of the signal processing circuits 123 adjacent to the region of the pixel region, and is adjacent to the pixel region. The other signal processing circuit 123 of the other area processes the remaining half (e.g., even columns).

[Examples]

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the following examples as long as the scope of the invention is not exceeded. In addition, "part" is a quality standard unless otherwise specified.

<Synthesis of Polymer>

<Synthesis Example 1 - Polymer 1>

A solution of the following composition was prepared in a monomer dropping container.

A solution of the following contents was prepared in a container for dropping a chain transfer agent.

To the reaction vessel (separable flask with a cooling tube), 188 parts of diethylene glycol dimethyl ether was added, and after nitrogen substitution, heating was carried out to raise the temperature of the reaction vessel to 90 °C.

After confirming that the temperature was stable, the monomer dropping container and the chain transfer agent dropping container were gradually dropped into the reaction container, and the monomer and chain transfer agent were added dropwise at 140 ° C for 140 minutes. .

After 60 minutes from the end of the dropwise addition, the temperature was further raised, the temperature of the reaction vessel was raised to 110 ° C, and the temperature was directly maintained at 110 ° C for 180 minutes. Thereafter, the inside of the reaction vessel was replaced with air.

Then, a compound of the following composition was placed in a reaction container, and reacted at a temperature of 110 ° C for 9 hours.

After the completion of the reaction, 27 parts of diethylene glycol dimethyl ether was added, and the mixture was cooled to room temperature to obtain a polymer 1.

<Synthesis Example 2 - Polymer 2>

A solution of the following composition was prepared in a monomer dropping container.

A solution of the following contents was prepared in a container for dropping a chain transfer agent.

To the reaction vessel (separable flask with a cooling tube), 188 parts of diethylene glycol dimethyl ether was added, and after nitrogen substitution, heating was carried out to raise the temperature of the reaction vessel to 90 °C.

After confirming that the temperature was stable, the monomer dropping container and the chain transfer agent dropping container were gradually dropped into the reaction container, and the monomer and chain transfer agent were added dropwise at 140 ° C for 140 minutes. .

After 60 minutes from the end of the dropwise addition, the temperature was further raised, the temperature of the reaction vessel was raised to 110 ° C, and the temperature was directly maintained at 110 ° C for 180 minutes. Thereafter, the inside of the reaction vessel was replaced with air.

Then, a compound of the following composition was placed in a reaction container, and reacted at a temperature of 110 ° C for 9 hours.

. GMA 43

After the completion of the reaction, 39 parts of diethylene glycol dimethyl ether was added, and cooled to room temperature to obtain a polymer 2.

<Synthesis Example 3 - Polymer 3>

A solution of the following composition was prepared in a monomer dropping container.

A solution of the following contents was prepared in a container for dropping a chain transfer agent.

To the reaction vessel (separable flask with a cooling tube), 188 parts of diethylene glycol dimethyl ether was added, and after nitrogen substitution, heating was carried out to raise the temperature of the reaction vessel to 90 °C.

After confirming that the temperature was stable, the monomer dropping container and the chain transfer agent dropping container were gradually dropped into the reaction container, and the monomer and chain transfer agent were added dropwise at 140 ° C for 140 minutes. .

After 60 minutes from the end of the dropwise addition, the temperature was further raised, the temperature of the reaction vessel was raised to 110 ° C, and the temperature was directly maintained at 110 ° C for 180 minutes. Thereafter, The inside of the reaction vessel was replaced with air.

Then, a compound of the following composition was placed in a reaction container, and reacted at a temperature of 110 ° C for 9 hours.

After completion of the reaction, it was cooled to room temperature to obtain a polymer 3.

The solid content of the polymer 1 to the polymer 3 obtained in the above Synthesis Example was measured. Further, the components derived from the respective raw material monomers were analyzed by ¹ H-NMR. Further, the weight average molecular weight was measured by GPC. The evaluation results are shown in Table 1 below.

<Example 1> Formation of a transparent pattern of a color filter for a solid-state imaging element

<Preparation of a resist liquid for a flattening film>

The following components were mixed and stirred by a homomixer to prepare a resist liquid for a planarizing film.

The flattening film is composed of a resist liquid

. Propylene glycol monomethyl ether acetate solution of benzyl methacrylate/methacrylic acid (=70/30 [mole ratio]) copolymer (20%, weight average molecular weight: 30,000, manufactured by Fujikura Kasei Co., Ltd., product name) For Acrybase FF-187)...22 servings

. Dipentaerythritol hexaacrylate...6.5 parts

(Manufactured by Nippon Kayaku Co., Ltd., the product name is KAYARAD DPHA)

. Propylene glycol monomethyl ether acetate (manufactured by Daicel Chemical Co., Ltd., product name: MMPGAC)...13.8 parts

. Ethyl-3-ethoxypropionate (manufactured by Changchun Industry Co., Ltd., product name is ethyl-3-ethoxypropionate)...12.3 parts

. Halomethyltriazine compound (Compound I below) (manufactured by PANCHIM, the product name is triazine PP)...0.3 parts

<Production of flattening film>

The above-mentioned planarizing film obtained was applied onto a 6-inch wafer by spin coating. Then, heat treatment was performed on the hot plate at a surface temperature of 100 ° C for 120 seconds, and a coating film having a uniform film thickness of about 1.0 μm was obtained on the above-mentioned tantalum wafer. Following Then, the coated film was subjected to a hardening treatment at 230 ° C for 1 hour in an oven to obtain a planarized film.

<Preparation of Radiation-Linear Composition>

The radiation sensitive composition of the present invention was prepared by stirring and mixing the following components using a magnetic stirrer.

Composition of a radioactive linear composition

<Production of Coating Film>

The radiation sensitive composition obtained in the above manner was applied onto the flattening film of the tantalum wafer by spin coating, and then heated at 120 ° C on the surface of the coated film surface by a heating plate for 120 seconds. The film was dried to form a coated film having a film thickness of about 0.8 μm after drying.

<Formation of Transparent Pattern of Color Filter for Solid Photographic Element>

Then, using an i-ray stepper (FPA-3000i5+ manufactured by Canon), the mask pattern in a 4 mm × 3 mm area on the substrate was respectively arranged via a 1.2 μm square pixel, at 100 mJ. The exposure amount of /cm ² was exposed to the dried coating film.

The pattern-exposed coating film was subjected to puddle development for 60 seconds at room temperature using a 60% aqueous solution of an organic alkaline developer CD-2000 (Fujifilm Electronic Materials Co., Ltd.). Then, it is rinsed with pure water for 20 seconds by rotary spraying. Thereafter, it is further washed with pure water. Thereafter, the water droplets are made to fly out by the high-pressure air, and the substrate is naturally dried, and then The hot plate was subjected to post-baking treatment at 220 ° C for 300 seconds to form a transparent pattern on the tantalum wafer.

In the above manner, making 1.0 μm on the flattening film of the above-mentioned silicon wafer A transparent pattern of squares is obtained to obtain a transparent pattern of color filters for solid-state imaging elements.

Then, the radiation sensitive composition was applied to Corning 1737 (manufactured by Corning) under the same conditions as those for forming a transparent pattern on the flattened film of the above-described ruthenium wafer to form a coating film, which was sequentially applied. This coating film was subjected to respective treatments of total exposure, development, rinsing, water washing, and post-baking to form a transparent film having a film thickness of 1 μm, which was used as a transmittance measurement sample.

Then, the transmittance of the transparent film was measured using MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). All regions in the wavelength range from 400 nm to 700 nm have a transmittance of 93% or more.

<evaluation>

The transparent pattern on the flattening film of the above-described ruthenium wafer obtained as described above was subjected to the following evaluation and measurement. The results of the evaluation and measurement are shown in the following table.

Residue

Using a Scanning Electron Microscope (SEM) (S-7800H, manufactured by Hitachi, Ltd.), it was observed from the top of the color filter on the wafer at 30,000 times and then baked. The pixel pattern of the color filter (1.0 μm square) was evaluated for the presence or absence of residue under visual observation according to the following evaluation criteria.

The less the development residue, the more excellent the resolution of the pattern.

5: 5 or less

4:6~10

3:11~20

2:21~50

1:51 or more

Size uniformity

In the square pixel in the 1/3 inch area on the substrate (4.8 mm × 3.6 mm, hereinafter referred to as "shot"), the pattern of the center portion and the end portion (corner portion) was measured. The difference in size. Specifically, the absolute value |Δa | (=| a1 - a2 |) of the difference between the pattern size a1 of the pattern center portion in the pattern and the pattern size a2 at the end portion in one shot is measured. Fig. 3 is a conceptual diagram showing a central portion and an end portion of a square pixel in one shot.

The evaluation was performed based on the following criteria.

5:| △a |≦0.01

4:0.01<| △a |≦0.03

3:0.03<| △a |≦0.05

2:0.05<| △a |≦0.10

1:0.10<| △a |

Line width change after delay after exposure

The pattern size b1 when the pattern was formed by continuing the exposure step after coating, and the pattern size b2 when the pattern was formed after the coating step was carried out for 72 hours, and then the exposure step was performed, and the measurement was performed in the same manner as the dimensional stability described above. And find the value of Δb (= b1 - b2), and evaluate the absolute value of the difference | Δb | as follows.

5:| △b |≦0.01

4:0.01<| △b |≦0.03

3:0.03<| △b |≦0.05

2:0.05<| △b |≦0.10

1:0.10<| △b |

<Other Examples, Comparative Examples>

In the above-mentioned Example 1, the type of the polymer and the type of the polymerizable compound were changed in the same manner as described below, and the radiation sensitive compositions of the examples and the comparative examples were obtained.

M/B represents a (meth) acrylate compound having an acid group and a difunctional or higher number / all polymers × 100.

. Polymer 4: manufactured by Daicel Chemical Industries, Cyclomer ACA230AA

. Polymerizable Compound 2 (TO-2349, manufactured by East Asia Synthetic, polyfunctional acrylate compound containing acid group)

. Polymerizable Compound 3 (A-DPH-12E, manufactured by Shin-Nakamura Chemical Industry, an acid-free polyfunctional acrylate compound)

. Polymerizable Compound 4 (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., acid-free polyfunctional acrylate compound)

. Polymeric Compound 5 (Aronix M-305, manufactured by East Asia Synthetic, polyfunctional acrylate compound containing acid groups)

As shown in the above table, it is understood that when the radiation sensitive composition contains a polymer represented by the general formula (ED) and a trifunctional or tetrafunctional (meth) acrylate compound having an acid group, less residue can be obtained. A cured film having excellent dimensional uniformity and a change in line width after delay after exposure. In particular, it is understood that the total ratio of the polymer to the total amount of the acid group and the difunctional or higher (meth) acrylate (the acid group and the difunctional or higher (meth) acrylate / all polymer) When it is in the range of 1% by mass to 50% by mass, the residue becomes less.

In particular, it is highly effective from the viewpoint of obtaining a cured film having a small residue, uniformity of size, and a change in line width after post-exposure delay at a level of a pattern size of 1.0 μm square.

In the above embodiments, an example of a transparent pattern in which a color filter is formed on a germanium wafer has been described. However, when a solid-state imaging device is fabricated, the germanium wafer is replaced with a photodiode. Light-shielding film, component protective film, etc. The substrate for a solid-state imaging element may be used.

For example, a tungsten-containing light-shielding film that opens only to the light-receiving portion of the photodiode is formed on the germanium wafer on which the photodiode and the transfer electrode are formed to cover the entire surface of the formed light-shielding film and the photodiode An element protective layer containing tantalum nitride is formed in a body light receiving portion (an opening portion in the light shielding film). Then, on the formed element protective layer, a transparent pattern (transparent pixel) is formed by the same method as the above embodiment, and red pixels, blue pixels, and green pixels are formed by a known method. And made a color filter. Then, a microlens as a concentrating device is formed on the obtained color filter, whereby a solid-state imaging device (CCD, CMOS, organic CMOS, or the like) having good color reproducibility can be produced.

100‧‧‧Photographic components

101‧‧‧Substrate

102‧‧‧Insulation

103‧‧‧Connecting electrode

104‧‧‧pixel electrodes

105, 106‧‧‧Connecting Department

107‧‧‧Organic layer

108‧‧‧ opposite electrode

109‧‧‧buffer layer

110‧‧‧ Sealing layer

111‧‧‧Color filters

112‧‧‧ partition wall

113‧‧‧Lighting layer

114‧‧‧Protective layer

115‧‧‧ Counter electrode voltage supply unit

116‧‧‧Readout circuit

R1‧‧‧1st area

Claims (18)

A radiation sensitive composition comprising a polymer, a polymerizable compound, and a polymerization initiator, and comprising a polymer obtained by polymerizing a monomer component containing a compound represented by the following formula (ED) as the above The polymer contains a (meth) acrylate compound having an acid group and a difunctional or higher functional group as the polymerizable compound, and the content of the coloring agent in the total solid content of the radiation sensitive composition is 3.0% by mass or less. (In the general formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent). The radiation-sensitive composition according to claim 1, wherein the ratio of the (meth) acrylate compound having an acid group and having a difunctional or higher (the above-mentioned acid group) is The difunctional or higher (meth) acrylate compound / all of the above polymers × 100) is in the range of 1% by mass to 50% by mass. The radiation-sensitive linear composition described in claim 1 of the patent application A polymerizable compound other than the above (meth) acrylate compound having an acid group and having a difunctional or higher functional group is used as the above polymerizable compound. The radiation sensitive composition according to the second aspect of the invention, further comprising the polymerizable compound other than the (meth) acrylate compound having an acid group and having a difunctional or higher functional group as the polymerizable compound. The radiosensitive linear composition according to the third aspect of the invention, wherein the ratio of the (meth) acrylate compound having an acid group and having a difunctional or higher functional group is from 1% by mass to 50% by mass. . The radiation-sensitive linear composition according to the fourth aspect of the invention, wherein the ratio of the (meth) acrylate compound having an acid group and having a difunctional or higher functional group is 1% by mass to 50% by mass. . The radiation sensitive composition according to any one of claims 1 to 6, further comprising at least 1 selected from the group consisting of an ultraviolet absorber, a solvent, a adhesion improver, a polymerization inhibitor, and a surfactant. Kind. The radiation sensitive composition according to any one of claims 1 to 6, which does not contain the above coloring agent. A cured film formed by curing the radiation sensitive composition according to any one of claims 1 to 6. A color filter comprising a coloring layer formed by curing the radiation sensitive composition according to any one of claims 1 to 6. A method for producing a cured film, comprising: (1) a sensation according to any one of claims 1 to 6 a step of applying the radioactive composition to the substrate; (2) a step of exposing the applied radiation sensitive composition; (3) a step of developing the exposed radiation sensitive composition; and (4) a post-baking step of thermally curing the above-described developed radiation-sensitive composition. A method of producing a color filter, comprising: (1) a step of applying a radiation-sensitive composition according to any one of claims 1 to 6 to a substrate; (2) a step of exposing the above-described radiation sensitive composition to be applied; (3) a step of developing the exposed radiation sensitive composition; and (4) performing the developed radiation sensitive composition A post-baking step of heat hardening. A solid-state photographic element comprising the color filter of claim 10 of the patent application. A liquid crystal display device comprising the color filter according to claim 10 of the patent application. An organic electroluminescence display device comprising the color filter according to claim 10 of the patent application. A solid-state photographic element comprising a color filter manufactured by the method of producing a color filter according to claim 12 of the patent application. A liquid crystal display device comprising a color filter manufactured by the method for producing a color filter according to claim 12 of the patent application. An organic electroluminescence display device comprising a color filter manufactured by the method for producing a color filter according to claim 12 of the patent application.