JP6524786B2 - Positive radiation sensitive resin composition, infrared shielding film, method for forming the same, solid-state imaging device, illuminance sensor - Google Patents

Description

  The present invention relates to a positive radiation sensitive resin composition, an infrared shielding film, a method of forming the same, a solid-state imaging device, and an illuminance sensor.

  A CMOS image sensor chip which is a solid-state image sensor of a color image is used for a smartphone, a video camera and the like. Since these solid-state imaging devices use silicon photodiodes having sensitivity to near infrared light in their light receiving portions, visibility correction is required, and an infrared cut filter is used (see, for example, Patent Document 1).

In addition, an illuminance sensor is mounted on a smartphone or the like, and is used to adjust the brightness of a screen indoors or outdoors, and an infrared cut filter is used (see, for example, Patent Document 2).
However, when the surface of the solid-state imaging device substrate or the like faces the infrared cut filter with a space in between as described above, the incident angle dependency of the light received by the solid-state imaging device becomes large, which causes the malfunction. Could be a problem.
In order to reduce the incident angle dependency of the infrared cut filter, an attempt has been made to form a film of a curable resin composition on a substrate (see, for example, Patent Document 3).

However, these curable resin compositions have difficulty in forming a pattern of an infrared shielding film with high sensitivity and good patterning properties.
From these viewpoints, from the viewpoint of improving the productivity of solid-state imaging devices and illumination sensors, pattern formation of an infrared shielding film can be formed with high sensitivity, and a positive radiation-sensitive resin composition excellent in patterning properties is required.

JP, 2012-28620, A JP, 2011-60788, A JP 2012-189632 A

  The present invention has been made based on the above circumstances, and an object thereof is to form a pattern of an infrared shielding film with high sensitivity, and to have a positive type sensitivity excellent in shielding property, chemical resistance and refractive index. It is an object of the present invention to provide a radiation-sensitive resin composition, a solid-state imaging device having an infrared shielding film formed from the positive radiation-sensitive resin composition, an illuminance sensor, and a method of forming an infrared shielding film.

The invention made to solve the above problems is
This is achieved by a positive-working radiation-sensitive resin composition containing [A] alkali-soluble resin, [B] quinonediazide compound, and [C] infrared shielding material, and further, [A] polymer is in the same or different polymer molecule. And a positive type radiation sensitive resin composition which is a polymer having a structural unit containing a carboxyl group and a structural unit containing a crosslinkable group.

  Moreover, another invention made in order to solve the said subject is achieved by the infrared rays shielding film formed from the said positive radiation sensitive resin composition, the solid-state image sensor which has the said infrared rays shielding film, or an illumination intensity sensor.

  Further, a step of forming a coating on a substrate, a step of irradiating at least a part of the coating, a step of developing the coating irradiated with the radiation, and a step of heating the developed coating In the method of forming an infrared shielding film, the coating film is formed by using the positive type radiation sensitive resin composition of the present invention.

The present invention has been made based on the above circumstances, and an object thereof is to form a pattern of infrared shielding film with high sensitivity and to be positive type excellent in infrared shielding property, chemical resistance and refractive index. It is an object of the present invention to provide a radiation-sensitive resin composition, a solid-state imaging device having an infrared shielding film formed from the positive radiation-sensitive resin composition, an illuminance sensor, and a method of forming an infrared shielding film. .
It is possible to provide an infrared shielding film formed from the positive radiation-sensitive resin composition, a method for forming the same, and a solid-state imaging device provided with the infrared shielding film.
Therefore, the said positive radiation sensitive resin composition, the said infrared rays shielding film, and its formation method can be used suitably for manufacturing processes, such as a solid-state image sensor and an illumination intensity sensor.

It is the schematic which shows the structure of the camera module provided with the solid-state image sensor of embodiment of this invention. It is the schematic which shows the structure of the illumination intensity sensor of embodiment of this invention.

<Positive radiation sensitive resin composition>
The positive-working radiation-sensitive resin composition of the present invention is a positive-working radiation-sensitive resin composition containing [A] an alkali-soluble resin, a [B] quinonediazide compound, and a [C] infrared shielding material. It is not particularly limited as long as it is a polymer, and a polymer having developability is preferable from the viewpoint of pattern formation. As such a particularly preferable polymer, a polymer having a structural site having a phenolic hydroxyl group, a carboxyl group, a silanol group or the like is preferable. As such an alkali-soluble resin, acrylic resins, novolac resins, polyamic acids, polyimides, polybenzoxazoles, polysiloxanes, polyethers and the like are preferable, and in particular, acrylic resins, novolac resins, polyamic acids and polyimides are selected. At least one polymer is preferred.
The alkali-soluble resin is particularly preferably a polymer having a structural unit containing a carboxyl group and a crosslinkable group-containing structural unit in the same or different polymer molecules.
Furthermore, the said positive radiation sensitive resin composition may contain other arbitrary components in the range which does not impair the effect of this invention. Each component will be described in detail below.

<[A] Alkali-Soluble Resin>
The [A] alkali-soluble resin contained in the positive-working radiation-sensitive resin composition of the present embodiment is a resin soluble in an alkaline solvent, and is a resin having alkali developability. [A] The alkali-soluble resin is preferably, for example, one selected from an acrylic resin having a carboxyl group, a polyimide resin, a polysiloxane, and a novolac resin. Hereinafter, each of an acrylic resin having a carboxyl group, a polyimide resin, a polysiloxane and a novolac resin will be described in more detail.
[Acryl resin having a carboxyl group]
It is preferable that the acrylic resin which has a carboxyl group is what contains the structural unit which has a carboxyl group, and the structural unit which has a polymeric group. In that case, it is not particularly limited as long as it contains a structural unit having a carboxyl group and a structural unit having a polymerizable group and has alkali developability (alkali solubility).

  The structural unit having a polymerizable group is preferably at least one structural unit selected from the group consisting of a structural unit having an epoxy group and a structural unit having a (meth) acryloyloxy group. The acrylic resin which has a carboxyl group can form the film which has the outstanding surface curability and deep part curability by including the said specific structural unit, and can form the cured film of embodiment of this invention.

  The structural unit having a (meth) acryloyloxy group is, for example, a method of reacting (meth) acrylic acid with an epoxy group in a copolymer, (meth) acrylic acid ester having an epoxy group in a carboxyl group in a copolymer By reacting (meth) acrylic acid ester having isocyanate group with hydroxyl group in the copolymer, or by reacting (meth) acrylic acid hydroxy ester with acid anhydride site in the copolymer, etc. It can be formed. Among these, a method of reacting a (meth) acrylic acid ester having an epoxy group with a carboxyl group in a copolymer is particularly preferable.

  An acrylic resin containing a structural unit having a carboxyl group and a structural unit having an epoxy group as a polymerizable group is at least one selected from the group consisting of (A1) unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter referred to as It can synthesize | combine and synthesize | combine "(A1) compound".) And (A2) epoxy group containing unsaturated compound (Hereafter, it is also called "(A2) compound."). In this case, the acrylic resin having a carboxyl group is a structural unit formed from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a structural unit formed from an epoxy group-containing unsaturated compound And a copolymer containing

For example, an acrylic resin having a carboxyl group is copolymerized with a compound (A1) giving a carboxyl group-containing constitutional unit and a compound (A2) giving an epoxy group-containing constitutional unit in the presence of a polymerization initiator in a solvent. It can be manufactured by In addition, it is possible to further add (A3) a hydroxyl group-containing unsaturated compound (hereinafter, also referred to as "(A3) compound") giving a hydroxyl group-containing constitutional unit to obtain a copolymer. Furthermore, in the production of the acrylic resin having a carboxyl group, the compound (A4) (the compound (A1), the compound (A2) and the compound (A3) together with the compound (A1), the compound (A2) and the compound (A3) described above The unsaturated compound which gives structural units other than the structural unit derived from a compound) can be further added, and it can be set as a copolymer. Next, each compound of (A1) to (A3) will be described in detail.
((A1) compound)
Examples of the compound (A1) include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, mono [(meth) acryloyloxyalkyl] esters of polyhydric carboxylic acids, and the like.

  As unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid etc. are mentioned, for example.

  Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like.

  As an anhydride of unsaturated dicarboxylic acid, the anhydride of the compound illustrated as said dicarboxylic acid etc. are mentioned, for example.

  Among these (A1) compounds, acrylic acid, methacrylic acid and maleic anhydride are preferable, and acrylic acid, methacrylic acid and maleic anhydride are more preferable from the viewpoint of copolymerization reactivity, solubility in an alkaline aqueous solution and availability.

  These (A1) compounds may be used alone or in combination of two or more.

The use ratio of the compound (A1) is preferably 5% by mass to 30% by mass based on the total of the compound (A1) and the compound (A2) (optionally, the optional compound (A3) and compound (A4)). And 10% by mass to 25% by mass are more preferable. By setting the use ratio of the compound (A1) to 5% by mass to 30% by mass, the solubility of the acrylic resin having a carboxyl group in an aqueous alkaline solution can be optimized, and a film excellent in radiation sensitivity can be formed. .
((A2) compound)
The compound (A2) is an epoxy group-containing unsaturated compound having radical polymerization. As an epoxy group, oxiranyl group (1, 2- epoxy structure) or oxetanyl group (1, 3- epoxy structure) etc. are mentioned.

Examples of unsaturated compounds having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, and 6,7 acrylic acid. -Epoxy heptyl, methacrylic acid 6, 7-epoxy heptyl, α-ethyl acrylic acid-6, 7-epoxy heptyl, o-vinyl benzyl glycidyl ether, m- vinyl benzyl glycidyl ether, p- vinyl benzyl glycidyl ether, methacrylic acid 3 , 4-epoxycyclohexylmethyl and the like. Among these, glycidyl methacrylate, 2-methyl glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, methacrylic acid 3, 4-epoxycyclohexyl, 3,4-epoxycyclohexyl acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate, etc. have copolymerization reactivity and solvent resistance such as insulating film It is preferable from the viewpoint of improvement of

Examples of unsaturated compounds having an oxetanyl group include
3- (Acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyl oxetane, 3- (acryloyloxymethyl) -2-phenyl oxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2-ethyl oxetane, 3- (2-acryloyloxyethyl) -3-ethyl oxetane, 3- (2-acryloyloxyethyl) -2 -Acrylic acid esters such as phenyl oxetane;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyl oxetane, 3- (methacryloyloxymethyl) -2-phenyl oxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyl oxetane, 3- (2-methacryloyloxyethyl) -3-ethyl oxetane, 3- (2-methacryloyloxyethyl) -2 -Methacrylic acid esters such as phenyloxetane and 3- (2-methacryloyloxyethyl) -2, 2-difluorooxetane, and the like can be mentioned.

Among these (A2) compounds, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate, 3- (methacryloyloxymethyl) ) 3-Ethyl oxetane is preferred. These (A2) compounds may be used alone or in combination of two or more.

The proportion of the compound (A2) used is preferably 5% by mass to 60% by mass, based on the total of the compound (A1) and the compound (A2) (optionally any compound (A3) and compound (A4)). And 10% by mass to 50% by mass are more preferable. By setting the use proportion of the compound (A2) to 5% by mass to 60% by mass, a cured film of the present embodiment having excellent curability and the like can be formed.
((A3) compound)
Examples of the compound (A3) include (meth) acrylic acid ester having a hydroxyl group, (meth) acrylic acid ester having a phenolic hydroxyl group, and hydroxystyrene.

  Examples of the acrylic acid ester having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate and the like.

  Examples of the methacrylic acid ester having a hydroxyl group include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate and the like.

  As an acrylic ester having a phenolic hydroxyl group, 2-hydroxyphenyl acrylate, 4-hydroxyphenyl acrylate and the like can be mentioned. Examples of the methacrylic acid ester having a phenolic hydroxyl group include 2-hydroxyphenyl methacrylate and 4-hydroxyphenyl methacrylate.

  As hydroxystyrene, o-hydroxystyrene, p-hydroxystyrene and α-methyl-p-hydroxystyrene are preferable. These (A3) compounds may be used alone or in combination of two or more.

The proportion of the compound (A3) used is preferably 1% by mass to 30% by mass, based on the total of (A1) compound, (A2) compound and (A3) compound (optional (A4) compound as required) And 5% by mass to 25% by mass are more preferable.
((A4) compound)
The compound (A4) is not particularly limited as long as it is an unsaturated compound other than the compounds (A1), (A2) and (A3) described above. As the compound (A4), for example, methacrylic acid linear alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid linear alkyl ester, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester And maleimide compounds, unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton and the like, and other unsaturated compounds.

  These (A4) compounds may be used alone or in combination of two or more. The use ratio of the compound (A4) is preferably 10% by mass to 80% by mass based on the total of the compound (A1), the compound (A2) and the compound (A4) (and the optional compound (A3)).

As specific examples and polymerization methods of these monomers, it is possible to polymerize by a known method, and it is possible to polymerize by patent 2961722 patent, patent 3241399 patent, patent 5607364 patent, patent 3838626 patent, patent 4853228 The gazette, the patent 4947300 gazette, the patent 5002275 gazette etc. can be referred to.
[Polyimide resin]
A preferred polyimide resin as the [A] alkali-soluble resin used for the positive-working radiation-sensitive resin composition of the present embodiment is a group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and a thiol group in the constituent units of the polymer. It is a polyimide resin having at least one selected from the group consisting of By having such an alkali-soluble group in the structural unit, an alkali developability (alkali solubility) can be provided, and the scum expression in the exposed area can be suppressed at the time of alkali development.

  In addition, it is preferable that the polyimide resin has a fluorine atom in the structural unit, because when the film is developed with an alkaline aqueous solution, water repellency is imparted to the interface of the film to suppress penetration of the interface and the like. The content of fluorine atoms in the polyimide resin is preferably 10% by mass or more in order to sufficiently prevent interface penetration, and 20% by mass or less in terms of solubility in an alkaline aqueous solution.

  A preferred polyimide resin as the alkali-soluble resin [A] used for the positive-working radiation-sensitive resin composition of the present embodiment is, for example, a polyimide resin obtained by condensation of an acid component and an amine component. It is preferable to select tetracarboxylic dianhydride as an acid component, and it is preferable to select diamine as an amine component.

  [A] The structure of the polyimide resin preferable as the alkali-soluble resin is not particularly limited, but it is preferable to have a structural unit represented by the following formula (I-1).

In the formula ^{(I-1), R} 1 is a tetravalent to 14-valent organic group, ^{R 2} represents a divalent to 12-valent organic group.
R ³ and R ^{4 each} represent a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group or a thiol group, which may be the same or different. a and b represent the integer of 0-10.

In the formula ^(I-1), R 1 represents the residue of a tetracarboxylic dianhydride used in the formation of a polyimide resin, a tetravalent to 14-valent organic group. Among them, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

  Examples of tetracarboxylic acid dianhydrides used for forming the polyimide resin include 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid dianhydride , 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenonetetra Carboxylic acid 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, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2 , 3-di Ruboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-di (di) Carboxyphenyl) hexafluoropropane dianhydride, 3,3 ′, 4,4′-diphenyl sulfone tetracarboxylic acid dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9 Preferred is 9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorene dianhydride or acid dianhydride having the structure shown below. Two or more of these may be used.

R ⁵ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ . R ⁶ and R ^{7 each} represent a hydrogen atom, a hydroxyl group or a thiol group.

In the above formula (I-1), R ² represents the residue of a diamine used to form the polyimide resin, a divalent to 12-valent organic group. Among them, an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferable.

  Specific examples of the diamine used to form the polyimide resin include 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone 3,4,4'-diaminodiphenylsulphide, 4,4'-diaminodiphenylsulphide, m-phenylenediamine, p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 9,9-bis ( 4-aminophenyl) fluorene or shown below Diamine of the structure is preferable. Two or more of these may be used.

R ⁵ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ . R ^{6 to} R ^{9 each} represent a hydrogen atom, a hydroxyl group or a thiol group.

Moreover, in order to form the coating film of the positive type radiation sensitive resin composition of this embodiment on a board | substrate and to improve the adhesiveness of the cured film and board | substrate formed after that, in the range which does not reduce heat resistance. , R ¹ or R ² may be copolymerized with an aliphatic group having a siloxane structure. Specifically, those obtained by copolymerizing 1 mol% to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, etc. as diamine which is an amine component It can be mentioned.

In the above formula (I-1), ^{R 3} and ^{R 4} represents a carboxyl group, a phenolic hydroxyl group, sulfonic acid group or a thiol group. a and b show the integer of 0-10. From the viewpoint of the stability of the positive-working radiation-sensitive resin composition to be obtained, a and b are preferably 0, but from the viewpoint of solubility in an aqueous alkali solution, a and b are preferably 1 or more.

By adjusting the amount of the alkali-soluble group of R ³ and R ^4, the dissolution rate in the alkaline aqueous solution is changed, so that the positive-type radiation-sensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment. it can.

When the above R ³ and R ⁴ are both phenolic hydroxyl groups, (a) polyimide resin is preferred in order to set the dissolution rate in an aqueous solution of 2.38 mass% tetramethylammonium hydroxide (TMAH) to a more appropriate range. It is preferable to contain 2 mol to 4 mol of the amount of phenolic hydroxyl groups in 1 kg of (a). By setting the amount of phenolic hydroxyl groups in this range, a positive type radiation sensitive resin composition with higher sensitivity and higher contrast can be obtained.

  Moreover, it is preferable that the polyimide which has a structural unit represented by said Formula (I-1) has an alkali-soluble group in the principal chain terminal. Such polyimides have high alkali solubility. Specific examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and a thiol group. The introduction of an alkali-soluble group to the main chain terminal can be carried out by providing an end-capping agent with an alkali-soluble group. As the end capping agent, monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, monoactive ester compounds and the like can be used.

  As monoamines used as an end capping agent, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy -4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene , 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4 -Aminobenzoic acid, 4-aminosalicylic acid, 5-amino Salicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4 -Aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like are preferable. Two or more of these may be used.

  Acid anhydrides, monocarboxylic acids, mono acid chloride compounds and mono active ester compounds used as end capping agents include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxy phthalate Acid anhydrides and other acid anhydrides, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1 -Hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and the like The Carboxylic acids and monoacid chloride compounds in which the carboxyl group is acid chlorided, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7- Monoacid chloride compounds in which only one carboxyl group of dicarboxylic acids such as dicarboxynaphthalene and 2,6-dicarboxynaphthalene is acid chlorided, monoacid chloride compounds and N-hydroxybenzotriazole, N-hydroxy-5-norbornene- The active ester compound etc. which are obtained by reaction with 2,3-dicarboximide are preferable. Two or more of these may be used.

  The introduction ratio of monoamine used for the end capping agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, preferably 60 mol% or less, particularly preferably 50 mol%, based on all amine components. It is less than mol%. The proportion of the acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound used as the end capping agent is preferably at least 0.1 mol%, particularly preferably 5 mol%, with respect to the diamine component. It is the above, Preferably it is 100 mol% or less, Especially preferably, it is 90 mol% or less. Multiple different end groups may be introduced by reacting multiple end capping agents.

  In the polyimide resin having a structural unit represented by the above formula (I-1), the repeating number of the structural unit is preferably 3 or more, more preferably 5 or more, preferably 200 or less, and more preferably 100 or less. Within this range, the photosensitive resin composition of the present embodiment can be used as a thick film.

  In the present embodiment, the polyimide resin preferable as the [A] alkali-soluble resin may be composed of only the structural unit represented by the above formula (I-1), or a copolymer with other structural units. Alternatively, it may be a mixture. In that case, it is preferable to contain 10 mass% or more of the structural units represented by General formula (I-1) of the whole polyimide resin. If it is 10% by mass or more, shrinkage at the time of heat curing can be suppressed, and it is suitable for producing a thick-film cured film. It is preferable to select the kind and quantity of the structural unit used for copolymerization or mixing in the range which does not impair the heat resistance of the polyimide resin obtained by final heat processing. For example, benzoxazole, benzimidazole, benzothiazole and the like can be mentioned. As for these structural units, 70 mass% or less in a polyimide resin is preferable.

  In the present embodiment, a preferred polyimide resin can be synthesized, for example, using a known method to obtain a polyimide precursor, and using a known imidization reaction method to imidate this. As a known synthesis method of a polyimide precursor, a part of diamine is replaced with a monoamine which is an end capping agent, or a part of an acid dianhydride is a monocarboxylic acid which is an end capping agent, acid anhydride It is obtained by reacting an amine component with an acid component in place of the monoacid chloride compound and the monoactive ester compound. For example, a method of reacting tetracarboxylic acid dianhydride and diamine (partially substituted with monoamine) at low temperature, tetracarboxylic acid dianhydride at low temperature (partially acid anhydride, mono acid chloride compound or monoactivity Method of reacting ester compound with diamine), method of obtaining diester with tetracarboxylic acid dianhydride and alcohol, and then reacting with diamine (partially substituted with monoamine) and condensing agent, tetracarboxylic acid There is a method of obtaining a diester with a dianhydride and an alcohol, thereafter acidifying the remaining dicarboxylic acid, and reacting with a diamine (a part of which is substituted with a monoamine).

Moreover, the imidization rate of the polyimide resin of this embodiment can be easily calculated | required by the following method, for example. First, measuring the infrared absorption spectrum of the polymer, absorption peaks of an imide structure caused by a polyimide (1780 cm around ^-1, 1377 cm around ^-1) to confirm the presence of. Next, the polymer is heat-treated at 350 ° C. for 1 hour, the infrared absorption spectrum is measured, and the content of the imide group in the polymer before heat treatment is calculated by comparing the peak intensities around 1377 cm ⁻¹ , and imidization Determine the rate.

  The imidation ratio of the polyimide resin in the present embodiment is preferably 80% or more from the viewpoint of chemical resistance and high shrinkage residual film ratio.

Moreover, the terminal blocker introduce | transduced into the polyimide resin preferable in this embodiment is easily detectable with the following method. For example, a polyimide resin into which a terminal blocking agent has been introduced is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component which are constituent units of the polyimide resin, and this is measured by gas chromatography (GC) or NMR Thus, the end capping agent used to form the polyimide resin can be easily detected. Apart from this, it is also easily detectable by directly measuring the polymer component to which the end capping agent has been introduced by pyrolysis gas chromatography (PGC) or infrared spectrum and ¹³ C-NMR spectrum.
[Polysiloxane]
A preferred polysiloxane as a resin used in the positive type radiation sensitive resin composition of the present embodiment is a polysiloxane having a radical reactive functional group. When the polysiloxane is a polysiloxane having a radical reactive functional group, it is not particularly limited as long as it has a radical reactive functional group in the main chain or side chain of the polymer of the compound having a siloxane bond. In that case, the polysiloxane can be cured by radical polymerization, and cure shrinkage can be minimized. As a radically reactive functional group, unsaturated organic groups, such as a vinyl group, (alpha)-methylvinyl group, acryloyl group, methacryloyl group, styryl group, are mentioned, for example. Among these, those having an acryloyl group or a methacryloyl group are preferable because the curing reaction proceeds smoothly.

  The preferred polysiloxane in this embodiment is a hydrolytic condensate of a hydrolyzable silane compound. The hydrolyzable silane compound constituting the polysiloxane is (s1) a hydrolyzable silane compound represented by the following formula (S-1) (hereinafter also referred to as (s1) compound), and (s2) a following formula (S) It is preferable that it is a hydrolysable silane compound containing the hydrolysable silane compound (Hereinafter, it is also mentioned a (s2) compound.) Shown by -2).

In the above formula ^{(S-1), R 11} is an alkyl group having 1 to 6 carbon atoms. R ¹² is an organic group containing a radical reactive functional group. p is an integer of 1 to 3; However, when R ¹¹ and R ¹² are plural, the plurality of R ¹¹ and R ¹² are each independent.

In the above formula ^{(S-2), R 13} is an alkyl group having 1 to 6 carbon atoms. R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a tolyl group, a naphthyl group, an epoxy group, an amino group or an isocyanate group. n is an integer of 0 to 20. q is an integer of 0 to 3; However, when R ¹³ and R ¹⁴ are plural, the plurality of R ¹³ and R ¹⁴ are each independent.

In the present invention, the "hydrolyzable silane compound" is usually hydrolyzed by heating within a temperature range of room temperature (about 25 ° C) to about 100 ° C in the coexistence of no catalyst and excess water. A compound having a group capable of forming a silanol group or a group capable of forming a siloxane condensate. In the hydrolysis reaction of the hydrolyzable silane compound represented by the above formula (S-1) and the above formula (S-2), some of the hydrolyzable groups are not hydrolyzed in the polysiloxane to be produced It may remain in the state. Here, the "hydrolyzable group" refers to a group that can be hydrolyzed to form a silanol group or a group that can form a siloxane condensate. In addition, in the positive-working radiation-sensitive resin composition of the present embodiment, some of the hydrolyzable silane compounds have some or all of the hydrolyzable groups in the molecule unhydrolyzed and others. It may remain in the form of a monomer without condensation with the hydrolyzable silane compound of In addition, a "hydrolysis condensation product" means the hydrolysis condensation product which some silanol groups of the hydrolyzed silane compound condensed. Hereinafter, the compounds (s1) and (s2) will be described in detail.
((S1) compound)
In the above formula ^{(S-1), R 11} is an alkyl group having 1 to 6 carbon atoms. R ¹² is an organic group containing a radical reactive functional group. p is an integer of 1 to 3; However, when R ¹¹ and R ¹² are plural, the plurality of R ¹¹ and R ¹² are each independent.

The alkyl group having 1 to 6 carbon atoms which is R ¹¹ described above, for example, a methyl group, an ethyl group, n- propyl group, i- propyl group, a butyl group. Among these, a methyl group and an ethyl group are preferable from the viewpoint of the ease of hydrolysis. As said p, 1 or 2 are preferable from a viewpoint of advancing of a hydrolysis condensation reaction, and 1 is more preferable.

As the organic group having a radical reactive functional group, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, in which one or more hydrogen atoms are substituted by the above-mentioned radical reactive functional group, carbon number Examples thereof include 6 to 12 aryl groups and aralkyl groups having 7 to 12 carbon atoms. When a plurality of R ¹² exist in the same molecule, they are each independent. The organic group represented by R ¹² may have a hetero atom. As such an organic group, an ether group, an ester group, a sulfide group etc. are mentioned, for example.

  Examples of the compound (s1) in the case of p = 1 include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, o-styryltrimethoxysilane, o-styryltriethoxysilane, m-styryltrimethoxysilane M-styryltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methacryloxytrimethoxysilane, methacryloxytriethoxysilane, methacryloxytripropoxysilane, Acryloxy trimethoxysilane, acryloxy triethoxysilane, acryloxy tripropoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, -Methacryloxyethyltripropoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acryloxyethyltrioxysilane Ethoxysilane, 2-acryloxyethyltripropoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane Methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane Trifluoro-butyl trimethoxy silane, 3-trialkoxysilane compounds such as (trimethoxysilyl) propyl succinic anhydride and the like.

  As the (s1) compound in the case of p = 2, for example, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, phenyltriethylsilane Dialkoxysilane compounds such as fluoropropyldimethoxysilane can be mentioned.

  As the (s1) compound in the case of p = 3, for example, allyldimethylmethoxysilane, allyldimethylethoxysilane, divinylmethylmethoxysilane, divinylmethylethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-acryloxypropyldimethylone Methoxysilane, 3-methacryloxypropyldiphenylmethoxysilane, 3-acryloxypropyldiphenylmethoxysilane, 3,3'-dimethacryloxypropyldimethoxysilane, 3,3'-diacryloxypropyldimethoxysilane, 3,3 ', Monoalkoxysilane compounds such as 3 ′ ′-trimethacryloxypropylmethoxysilane, 3,3 ′, 3 ′ ′-triacryloxypropylmethoxysilane, dimethyltrifluoropropylmethoxysilane It is below.

Among these (s1) compounds, since abrasion resistance and the like can be achieved at a high level, and condensation reactivity becomes high, vinyltrimethoxysilane, p-styryltriethoxysilane, 3-methacryloxypropyltrimethoxysilane Preferred are 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane and 3- (trimethoxysilyl) propyl succinic anhydride.
((S2) compound)
In the above formula ^{(S-2), R 13} is an alkyl group having 1 to 6 carbon atoms. R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a tolyl group, a naphthyl group, an epoxy group, an amino group or an isocyanate group. n is an integer of 0 to 20. q is an integer of 0 to 3; ^{However, if R 13} and ^{R 14} is each one, the plurality of ^{R 13} and ^{R 14} are each, independently.

As a C1-C6 alkyl group which is the above-mentioned R < ¹³ >, a methyl group, an ethyl group, n-propyl group, i-propyl group, a butyl group etc. are mentioned, for example. Among these, a methyl group and an ethyl group are preferable from the viewpoint of the ease of hydrolysis. As said q, 1 or 2 are preferable from a viewpoint of advancing of a hydrolysis condensation reaction, and 1 is more preferable.

When R ¹⁴ described above is an alkyl group having 1 to 20 carbon atoms, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a sec-butyl group. Group, tert-butyl group, n-pentyl group, 3-methylbutyl group, 2-methylbutyl group, 1-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group Group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2- Dimethylbutyl group, 1,1-dimethylbutyl group, n-heptyl group, 5-methylhexyl group, 4-methylhexyl group, 3-methylhexyl group, 2-methylhexyl group, 1- Hexylhexyl group, 4,4-dimethylpentyl group, 3,4-dimethylpentyl group, 2,4-dimethylpentyl group, 1,4-dimethylpentyl group, 3,3-dimethylpentyl group, 2,3-dimethylpentyl group 1,3-Dimethylpentyl, 2,2-dimethylpentyl, 1,2-dimethylpentyl, 1,1-dimethylpentyl, 2,3,3-trimethylbutyl, 1,3,3-trimethyl Butyl group, 1,2,3-trimethylbutyl group, n-octyl group, 6-methylheptyl group, 5-methylheptyl group, 4-methylheptyl group, 3-methylheptyl group, 2-methylheptyl group, 1- Methylheptyl group, 2-ethylhexyl group, n-nonanyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n Heptadecyl, n- hexadecyl group, n- heptadecyl group, n- octadecyl, n- nonadecyl group and the like. Preferably it is a C1-C10 alkyl group, More preferably, it is a C1-C3 alkyl group.

  Examples of the (s2) compound in the case of q = 0 include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetra-n-propoxysilane, and tetra-silane as tetrasilane compounds substituted with four hydrolyzable groups. -I-propoxysilane etc. are mentioned.

  Examples of the (s2) compound in the case of q = 1 include, as a silane compound substituted with one nonhydrolyzable group and three hydrolysable groups, for example, methyltrimethoxysilane, methyltriethoxysilane, Methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, naphthyl Trimethoxysilane, phenyltriethoxysilane, naphthyltriethoxysilane, aminotrimethoxysilane, aminotriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy, γ-glycidoxypropyltrimethoxysilane 3 isocyanoacetate trimethoxysilane, 3-isocyanoacetate triethoxysilane o- tolyl trimethoxysilane, m- tolyl trimethoxysilane p- tolyl trimethoxysilane, and the like.

  As the (s2) compound in the case of q = 2, as a silane compound substituted with two non-hydrolyzable groups and two hydrolysable groups, for example, dimethyldimethoxysilane, diphenyldimethoxysilane, ditolyl Dimethoxysilane, dibutyldimethoxysilane and the like can be mentioned.

  Examples of the (s2) compound in the case of q = 3 include, as a silane compound substituted with three non-hydrolyzable groups and one hydrolysable group, for example, trimethylmethoxysilane, triphenylmethoxysilane, and triphenylmethoxysilane. Tolyl methoxysilane, tributyl methoxysilane and the like can be mentioned.

  Among these (s2) compounds, silane compounds substituted with 4 hydrolyzable groups, and silane compounds substituted with 1 non-hydrolyzable group and 3 hydrolyzable groups are preferred, 1 More preferred are silane compounds substituted with one nonhydrolyzable group and three hydrolyzable groups. Particularly preferable hydrolyzable silane compounds include, for example, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, ethyltrit Methoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, naphthyltrimethoxysilane, γ-aminopropyltrimethoxysilane and γ-isocyanate Propyltrimethoxysilane is mentioned. You may use such a hydrolysable silane compound individually or in combination of 2 or more types.

The mixing ratio of the (s1) compound and the (s2) compound is desirably such that the (s1) compound exceeds 5 mol%. When the amount of the compound (s1) is 5 mol% or less, the exposure sensitivity at the time of forming a protective film as a cured film is low, and the scratch resistance and the like of the obtained protective film tend to be further reduced.
(Hydrolytic condensation of (s1) compounds and (s2) compounds)
As the conditions for hydrolytic condensation of the (s1) compound and the (s2) compound, at least a part of the (s1) compound and the (s2) compound is hydrolyzed to convert a hydrolysable group into a silanol group, and condensation is performed The reaction is not particularly limited as long as it causes a reaction, but can be carried out as follows, as an example.

  As water to be subjected to the hydrolysis and condensation reaction, it is preferable to use water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment, distillation and the like. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. The amount of water used is preferably 0.1 mol to 3 mol, more preferably 0.3 mol to 2 mol, per 1 mol of the total amount of hydrolyzable groups of the (s1) compound and the (s2) compound. Particularly preferably, it is 0.5 mol to 1.5 mol. By using such an amount of water, the reaction rate of hydrolytic condensation can be optimized.

  As a solvent to be subjected to hydrolytic condensation, for example, alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether Propionates, aromatic hydrocarbons, ketones, other esters and the like can be mentioned. These solvents can be used alone or in combination of two or more.

  Among these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, butyl butyl methoxyacetate are preferred, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate Propylene glycol monomethyl ether and butyl methoxyacetate are preferred.

  The hydrolysis condensation reaction is preferably an acid catalyst (eg, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resin, various Lewis acids, etc.), a base Catalysts (for example, nitrogen-containing compounds such as ammonia, primary amines, secondary amines, tertiary amines, and pyridines; basic ion exchange resins; hydroxides such as sodium hydroxide; carbonates such as potassium carbonate; It is carried out in the presence of a catalyst such as carboxylates such as sodium acetate; various Lewis bases etc. or alkoxides (eg zirconium alkoxide, titanium alkoxide, aluminum alkoxide etc). For example, tri-i-propoxyaluminum can be used as the aluminum alkoxide. The amount of the catalyst used is preferably 0.2 mol or less, more preferably 0.00001 mol to 0. 1 mol, per 1 mol of the monomer of the hydrolyzable silane compound, from the viewpoint of promoting the hydrolysis condensation reaction. It is 1 mole.

  As polystyrene conversion weight average molecular weight (henceforth "Mw" is called.) By GPC (gel permeation chromatography) of the above-mentioned hydrolysis condensation product, 500-10000 are preferred and 1000-5000 are more preferred. By setting Mw to 500 or more, the film formability of the positive type radiation sensitive resin composition of the present embodiment can be improved. On the other hand, by setting the Mw to 10000 or less, it is possible to prevent a decrease in the developability of the positive type radiation sensitive resin composition.

  As a polystyrene conversion number average molecular weight (henceforth "Mn" is called) by GPC of the above-mentioned hydrolysis condensation product, 300-5000 are preferable and 500-3000 are more preferable. By making Mn of polysiloxane into the said range, the hardening reactivity at the time of hardening of the coating film of positive type radiation sensitive resin composition of this embodiment can be improved.

As molecular weight distribution "Mw / Mn" of the said hydrolysis condensation product, 3.0 or less is preferable and 2.6 or less is more preferable. By setting the Mw / Mn of the hydrolysis condensate of the (s1) compound and the (s2) compound to 3.0 or less, the developability of the formed film can be enhanced. The positive-working radiation-sensitive resin composition of the present embodiment containing a polysiloxane can easily form a desired pattern shape with less occurrence of development residue during development.
[Novolak resin]
The novolak resin preferable as a resin used for the positive type radiation sensitive resin composition of this embodiment can be obtained by polycondensing phenols with aldehydes such as formalin by a known method.

  As phenols from which a preferable novolak resin is obtained in this embodiment, for example, phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2 , 4,5-Trimethylphenol, methylene bisphenol, methylene bis p-cresol, resorcinol, catechol, 2-methylresorcinol, 4-methylresorcinol, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol Phenol, m-methoxy , P-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, β-naphthol and the like can be mentioned. Two or more of these may be used.

  Further, in the present embodiment, as aldehydes for obtaining preferable novolak resins, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like can be mentioned besides formalin. Two or more of these may be used.

The weight average molecular weight of the novolak resin preferred as the resin used in the positive type radiation sensitive resin composition of the present embodiment is preferably 2000 to 50000, more preferably 3000 to 40000 in terms of polystyrene by GPC (gel permeation chromatography). It is.
<[B] quinone diazide compound>
The [B] quinone diazide compound which the said positive radiation sensitive resin composition can contain as a suitable component generate | occur | produces a carboxylic acid by irradiation of a radiation. The positive radiation-sensitive resin composition further includes a [B] quinone diazide compound, whereby a positive radiation-sensitive property in which the exposed part is removed in the developing step is added to the positive radiation-sensitive resin composition. It can be granted.

  [B] The quinone diazide compound preferably includes a condensate of a compound having a phenolic hydroxyl group and a naphthoquinone diazide sulfonic acid halide.

  As a compound which has a phenolic hydroxyl group, the compound etc. which are represented by a following formula are mentioned, for example.

  Among these, as compounds having a phenolic hydroxyl group, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 1,1,1 Preference is given to tri (p-hydroxyphenyl) ethane.

  Examples of the naphthoquinone diazide sulfonic acid halide include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-naphthoquinone diazide-5-sulfonic acid chloride. An ester compound (quinonediazide compound) obtained from 1,2-naphthoquinonediazide-4-sulfonic acid chloride is suitable for i-line exposure since it has absorption in the i-line (wavelength 365 nm) region. On the other hand, an ester compound (quinonediazide compound) obtained from 1,2-naphthoquinonediazide-5-sulfonic acid chloride is suitable for exposure in a wide range of wavelengths because absorption is present in a wide range of wavelength range.

  [B] As the quinonediazide compound, 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfone Preferred are condensates with acid chlorides, and condensates of 1,1,1-tri (p-hydroxyphenyl) ethane with 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

  [B] The Mw of the quinone diazide compound is preferably 300 to 1,500, more preferably 350 to 1,200. [B] By setting the Mw of the quinone diazide compound to 300 or more, the transparency of the interlayer insulating film to be formed can be maintained high. On the other hand, by setting the Mw of the [B] quinonediazide compound to 1,500 or less, it is possible to suppress the decrease in the pattern formation of the positive radiation-sensitive resin composition.

[B] The quinone diazide compounds can be used alone or in combination of two or more. The content of the [B] quinone diazide compound in the positive type radiation sensitive resin composition is preferably 1 part by mass to 100 parts by mass, more preferably 5 parts by mass with respect to 100 parts by mass of the [A] polyorganosiloxane. It is a mass part-50 mass parts. [B] By setting the content of the quinonediazide compound in the above specific range, the difference in solubility between the irradiated part and the non-irradiated part in the alkaline aqueous solution serving as the developer increases, and as a result, the patterning performance becomes good. In addition, the solvent resistance of the interlayer insulating film to be obtained also becomes good.
[C] Infrared shielding material As the infrared shielding material used in the present invention, any compound that absorbs light with a wavelength of 800 to 1200 nm can be used without particular limitation, and metal oxides, copper compounds, infrared rays It may be either an absorbing dye or an infrared absorbing pigment. Shielding means blocking a certain part of space from the influence of external force fields such as electric and magnetic fields, and an infrared shielding material means a compound having an effect of shielding the influence of infrared light.

  In the metal oxide used in the present invention, the infrared shielding material is described below from the viewpoint of resolution and sensitivity in pattern formation using a light source having a wavelength of 500 nm or less, as well as having high shielding properties to infrared light. Are more preferably tungsten compounds or metal borides, and most preferably tungsten compounds.

  Tungsten compounds are infrared shielding materials that have high absorption to infrared light (that is, high shielding properties to infrared light with a wavelength of about 800 to 1200 nm) and low absorption to visible light. When the curable composition for a solid-state imaging device of the present invention contains a tungsten compound, not only shielding property in the infrared region is high, but also a pattern can be formed with high sensitivity.

The tungsten compound may, for example, be a tungsten oxide compound, a tungsten boride compound or a tungsten sulfide compound, and the tungsten oxide compound represented by the following general formula (I) (composition formula) is more preferable. preferable.
MxWyOz (I)
M represents a metal, W represents tungsten, and O represents oxygen.

0.001 ≦ x / y ≦ 1.1
2.2 ≦ z / y ≦ 3.0
As the metal of M, alkali metals, alkaline earth metals, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Examples of the metal include Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, and Bi, and an alkali metal is preferable. One or more metals of M may be used.

  M is preferably an alkali metal, preferably Rb or Cs, and more preferably Cs.

  When x / y is 0.001 or more, infrared rays can be shielded sufficiently, and when 1.1 or less, generation of an impurity phase in the tungsten compound is more reliably avoided. it can.

  When z / y is 2.2 or more, the chemical stability as a material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the tungsten oxide compounds represented by the above general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like. Cs _0.33 WO ₃ or Rb _0.33 WO ₃ is preferable, and Cs _0.33 WO ₃ is more preferable.

  The tungsten compound is preferably in the form of fine particles. The average particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and still more preferably 200 nm or less. When the average particle diameter is in such a range, the tungsten fine particles are less likely to block visible light due to light scattering, and therefore, it is possible to make the light transmission in the visible light region more reliable. From the viewpoint of avoiding the photooxidation, the smaller the average particle size, the better. However, for reasons of ease of handling at the time of production, etc., the average particle size of the tungsten fine particles is usually 1 nm or more.

  Tungsten compounds are commercially available, but when the tungsten compound is, for example, a tungsten oxide compound, the tungsten oxide compound is obtained by a method of heat treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere (See Patent No. 4096205).

  In addition, a tungsten oxide-based compound is also available, for example, as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

  Similar to tungsten compounds, metal borides also have high absorption for infrared light (light with a wavelength of about 800 to 1200 nm) and low absorption for visible light, and are used for image formation; high pressure mercury lamp, KrF, The absorption is also smaller for short wave light than in the visible range used for exposure such as ArF. Therefore, if the curable composition for a solid-state imaging device of the present invention contains a metal boride, the shielding property in the infrared region is high and the light transmitting property in the visible light region is high, as in the case of containing the tungsten compound. , A pattern excellent in resolution and sensitivity can be obtained.

As metal borides, lanthanum boride (LaB ₆ ), praseodymium boride (PrB ₆ ), neodymium boride (N dB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), titanium boride TiB ₂ ), zirconium boride (ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), molybdenum boride (MoB) ₂ or 3 types such as Mo ₂ B ₅ , MoB), tungsten boride (W ₂ B ₅ ) and the like can be mentioned, and lanthanum boride (LaB ₆ ) is more preferable.

  The metal boride is preferably in the form of fine particles. The average particle diameter of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and still more preferably 100 nm or less. When the average particle diameter is in such a range, the metal boride fine particles are less likely to block visible light due to light scattering, so that it is possible to make the light transmission in the visible light region more reliable. From the viewpoint of avoiding the photooxidation, the smaller the average particle diameter, the better. However, for reasons of ease of handling at the time of production, etc., the average particle diameter of the metal boride fine particles is usually 1 nm or more.

The metal boride is available as a commercial product, for example, as a dispersion of metal boride fine particles such as KHF-7 manufactured by Sumitomo Metal Mining Co., Ltd.
The copper compound used in the present invention is not particularly limited as long as it is a copper compound having a maximum absorption wavelength in the range of wavelengths 700 nm to 1200 nm (near infrared region).

  The copper compound used in the present invention may or may not be a copper complex, but is preferably a copper complex.

  When the copper compound used in the present invention is a copper complex, the ligand L which coordinates to copper is not particularly limited as long as it can coordinate bond with a copper ion, but sulfonic acid, phosphoric acid, phosphoric ester, Compounds having phosphonic acid, phosphonic acid ester, phosphinic acid, phosphinic acid ester, carboxylic acid, carbonyl (ester, ketone), amine, amide, sulfonamide, urethane, urea, alcohol, thiol and the like can be mentioned. Among these, sulfonic acids, phosphoric acids, phosphoric esters, phosphonic acids, phosphonic esters, phosphinic acids and phosphinic esters are preferable, and sulfonic acids, phosphoric esters, phosphonic esters and phosphinic esters are more preferable.

  As a specific example of the copper compound used by this invention, a phosphorus containing copper compound, a sulfonic-acid copper compound, a carboxylic acid copper compound or the copper compound represented by the following general formula (A) is more preferable. As the phosphorus-containing compound, specifically, compounds described in WO 2005/030898 can be referred to, and the contents thereof are incorporated in the present specification.

  Hereinafter, the phosphate ester copper compound used in the present invention will be described in detail.

  The composition of the present invention preferably comprises a phosphate copper compound and an antioxidant. The composition of the present invention contains a phosphate ester copper compound, and is preferably contained in an amount of 20 to 95% by mass, and more preferably 30 to 80% by mass, with respect to the solid content of the composition. The number of phosphate ester copper compounds may be one, or two or more, and in the case of two or more, the total amount is in the above range.

The phosphate copper compound used in the present invention is preferably formed using a phosphate compound, and more preferably formed using a compound represented by the following formula (1).
Formula (1)
(HO) _n -P (= O)-(ORa ² ) _3-n
(Wherein, Ra ² is either an alkyl group, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 1 to 18 carbon atoms or alkenyl group having 1 to 18 carbon atoms, having 1 to 18 carbon atoms, -ORa ² Represents a polyoxyalkyl group having 4 to 100 carbon atoms, a (meth) acryloyloxyalkyl group having 4 to 100 carbon atoms, or a (meth) acryloyl polyoxyalkyl group having 4 to 100 carbon atoms, and n is 1 or When n is 1, Ra ² may be identical to or different from each other.

In the above formula, at least one of -ORa ² preferably represents a (meth) acryloyloxyalkyl group having 4 to 100 carbon atoms or a (meth) acryloyl polyoxyalkyl group having 4 to 100 carbon atoms, More preferably, it represents 4 to 100 (meth) acryloyloxyalkyl groups.

  The carbon number of the polyoxyalkyl group having 4 to 100 carbon atoms, the (meth) acryloyloxyalkyl group having 4 to 100 carbon atoms, or the (meth) acryloyl polyoxyalkyl group having 4 to 100 carbon atoms is 4 to 4 respectively. It is preferably 20, and more preferably 4 to 10.

In the formula (1), Ra ² is preferably an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and an alkyl group having 1 to 10 carbon atoms, an aryl having 6 to 10 carbon atoms It is more preferably a group, still more preferably an aryl group having 6 to 10 carbon atoms, and particularly preferably a phenyl group.

In the present invention, when n is 1, one of Ra ² is —ORa ² and a (meth) acryloyloxyalkyl group having 4 to 100 carbon atoms or a (meth) acryloyl poly having 4 to 100 carbon atoms preferably represents an oxy alkyl group, the other, the or a -ORa ^2, is preferably an alkyl group.

  Moreover, as a phosphoric acid ester compound of this invention, although phosphoric acid monoester (n = 2 in said Formula (1)) and phosphoric acid diester (n = 1 in said Formula (1)) are mentioned, From the viewpoint of infrared shielding properties and solubility, phosphoric acid diesters are preferred.

  The phosphate ester copper complex is in the form of a copper complex (copper compound) in which the phosphate ester is coordinated to the central metal copper. Copper in the phosphate ester copper complex is divalent copper, and can be produced, for example, by the reaction of a copper salt with a phosphate ester. Therefore, in the case of a near-infrared absorbing composition containing copper and a phosphoric acid ester compound, it is predicted that a phosphoric acid ester copper complex is formed in the composition.

  It is preferable that it is 300-1500, and, as for the molecular weight of the phosphate ester copper compound used by this invention, it is more preferable that it is 320-900.

  As a specific example of a phosphoric acid ester compound, the description of Unexamined-Japanese-Patent No. 2001-354945 can be considered into consideration, and these content is integrated in this-application specification. The description of International Publication WO 99/26952 pamphlet can be referred to for the synthesis method and preferable examples of the phosphate ester copper compound used in the present invention, and the contents of the specification are incorporated in the present specification.

Further, in the synthesis of the phosphate ester copper compound, as a commercial product, for example, phosphonic acids such as Phosmer M, Phosmer PE, Phosmer PP (manufactured by Uni Chemical Co., Ltd.) may be used.
As an infrared absorbing dye that can be used as an infrared shielding material in the present invention, cyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, immonium dyes, aminoum dyes, quinolium dyes, pyrilium dyes, Ni complex dyes, pyrrolopyrrole dyes, copper complexes, quaterrylene It is at least one selected from the group consisting of a dye, an azo dye, an anthraquinone dye, a dimonium dye, a squarylium dye and a porphyrin dye.

  Dyes that can be used as an infrared shielding material in the present invention are also commercially available, and for example, the following commercially available dyes are preferably mentioned.

FEW Chemicals S0345, S0389, S0450, S0253, S0322, S0585, S0402, S0391, S0094, S0325, S0260, S0229, S0447, S0378, S0306, S0484
American Dye Source, Inc. ----------------------------------------------A-A-A TDS, E. D.A.S. , ADS 840 MT, ADS 905 AM, ADS 956BP, ADS 1040 P, ADS 1040 T, ADS 1045 P, ADS 1040 P, ADS 1050 P, ADS 1065 A, ADS 1065 P, ADS 1100 T, ADS 1120 F
Yamamoto Chemical Co., Ltd. YKR-4010, YKR-3030, YKR-3070, MIR-327, MIR-371, SIR-159, PA-1005, MIR-369, MIR-379, SIR-128, PA-1006, YKR -2080, MIR-370, YKR-3040, YKR-3081, SIR-130, MIR-362, YKR-3080, SIR-132, PA-1001
Hayashibara Biochemical Research Institute NK-123, NK-124, NK-1144, NK-2204, NK-2268, NK-3027, NKX-113, NKX-1199, NK-2674, NK-3508, NKX-114, NK-2545, NK-3555, NK-3509, NK-3519
As a specific example of a cyanine type-dye and a quaterrylene type-dye, the compound as described in Unexamined-Japanese-Patent No. 2012-215806, 2008-009206 etc. is mentioned.

  As specific examples of the phthalocyanine compound, JP-A-60-224589, JP-A-2005-537319, JP-A-4-23868, JP-A-4-39361, JP-A-5-78364, and the like can be used. JP-A-5-222047, JP-A-5-222301, JP-A-5-222302, JP-A-5-345861, JP-A-6-25548, JP-A-6-107663, JP-A-6 JP-A-192584, JP-A-6-228533, JP-A-7-118551, JP-A-7-118552, JP-A-8-120186, JP-A-8-225751, JP-A-9-202860 Patent Publication Nos. 10-120927, 10-182995, and 11-35838. JP-A-2000-26748, JP-A-2000-63691, JP-A-2001-106689, JP-A-2004-18561, JP-A-2005-220060, and JP-A-2007-169343. Compounds are mentioned.

  As a specific example of an azo pigment, an anthraquinone pigment (anthraquinone compound), and a squarylium dye (squarylium compound), compounds described in JP 2012-215806 A and the like can be mentioned below.

  The above-mentioned dyes are also commercially available, and for example, Lumogen IR 765, Lumogen IR 788 (manufactured by BASF); ABS 643, ABS 654, ABS 667, ABS 670 T, IRA 693 N, IRA 735 (manufactured by Exciton); Examples include SDA3039, SDA3040, SDA3922, SDA7257 (manufactured by H. W. SANDS); TAP-15, IR-706 (manufactured by Yamada Chemical Industry), etc. In particular, as cyanine dyes, Daito chmix 1371F (manufactured by Daitoke Mix) And phthalocyanine dyes such as Excolor series, Excolor TX-EX 720, 708K (manufactured by Nippon Shokubai), etc. The present invention is not limited to Rugakore.

  These dyes may be used alone, but in order to express good shielding properties, two or more of them may be mixed and used according to the purpose.

  Examples of infrared absorbing pigments that can be used as an infrared shielding material in the present invention include zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, lead red, iron oxide red, yellow. Lead, zinc yellow (one zinc yellow, two zinc yellows), ultramarine blue, Prussia blue (ferrocyanide potassium), zircon gray, praseodymium yellow, chromium titanium yellow, chromium green, peacock, Victoria green, bituminous ( Vanadium zirconium blue, chromium tin pink, porcelain enamel, salmon pink, titanium black, tungsten compounds, metal borides, etc., and black pigments such as Co, Cr, Cu, Mn, Ru). 1 or 2 types selected from the group consisting of Fe, Ni, Sn, Ti and Ag Metal oxide containing metallic elements above, it is possible to use a metal nitrogen compounds or mixtures thereof.

  The content of the infrared shielding material is preferably 0.1% by mass or more and 50% by mass or less, and more preferably 1% by mass or more and 45% by mass, with respect to the total solid mass of the curable composition for a solid-state imaging device % Or less, more preferably 5% by mass or more and 40% by mass or less, and most preferably 5% by mass or more and 20% by mass or less. Moreover, it is possible to use 2 or more types of infrared shielding materials.

<Other optional components>
The said positive type radiation sensitive resin composition is a photoacid generator (except quinone diazide compound), antioxidant, polyfunctional acrylate, surfactant, adhesion adjuvant as needed in the range which does not impair the effect of the present invention. It may contain other optional components such as inorganic oxide particles, compounds having a cyclic ether group, solvents and the like. The other optional components may be used alone or in combination of two or more.
<Acid Generator (Excluding quinonediazide compounds>)
In the acid generator of the present invention, the acid generated from the acid generator upon irradiation with an actinic ray or radiation preferably generates an acid having a pKa of 3 or less. The acid generator may be a compound capable of generating an acid by heat. Examples of the acid generated from the acid generator upon irradiation with actinic rays or radiation include carboxylic acid, sulfonic acid, phosphoric acid, sulfinic acid, sulfuric acid, sulfuric acid, sulfuric acid, sulfuric acid monoester, hydrochloric acid, hexafluorophosphoric acid, tetrafluoroboric acid, etc. Grade boric acid etc. are mentioned. Examples of the compound capable of generating an acid include organic halogenated compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, and onium salt compounds.
As the organic halogenated compounds, specifically, Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), U.S. Pat. No. 3,905,815, JP-B-46-4605, Sho 48-36281, JP-A 55-32070, JP-A 60-239736, JP-A 61-169835, JP-A 61-169837, JP-A 62-58241, JP-A 62 No.-212401, JP-A-63-70243, JP-A-63-298339, M.I. P. The compound described in Hutt, Jurnal of Heterocyclic Chemistry, 1 (No 3), (1970) can be mentioned, and in particular, a trihalomethyl group-substituted oxazole compound: S-triazine compound can be mentioned.
More preferably, an s-triazine derivative in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to an s-triazine ring, specifically, for example, 2,4,6-tris (monochloromethyl)- s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl)- Examples include s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine and the like.
As the organic boron compound, for example, JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, JP-A2000- No. 131837, Japanese Patent Application Laid-Open No. 2002-107916, Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin, RadTech 9 8, Proceeding April 19-22, 1998, Chicago, etc. Organic borates, organic boron sulfonium complexes or organic boron oxo sulfonium complexes described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554, As described in JP-A-6-175553. Boron iodonium complexes, organic boron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527 Specific examples thereof include organic boron transition metal coordination complexes as described in Japanese Patent Application Laid-Open No. 7-292014.
As said disulfone compound, the compound described in Unexamined-Japanese-Patent No. 61-166544, 2002-328465 grade | etc., Is mentioned.
As said oxime ester compound, J.I. C. S. Perkin II (1979) 1653-1660), J. Org. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, but the compound of the compound described in JP-A 2000-66385 is preferable from the viewpoint of sensitivity. .
Examples of the onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.S. S. A diazonium salt described in Baletal, Polymer, 21, 423 (1980), an ammonium salt described in U.S. Pat. No. 4,069,055, JP-A-4-365049, etc., U.S. Pat. No. 4,069,055 No. 4,069, 056, phosphonium salts described in the respective specifications, European Patent Nos. 104, 143, U.S. Pat. Nos. 339, 049 and 410, 201, and Japanese Patent Laid-Open Nos. 2-150848. And iodonium salts described in JP-A-2-296514, European Patent Nos. 370, 693, 390, 214, 233, 567, 297, 443, 297, 442, U.S. Pat. No. 4,933,377, No. 161,811, No. 410,201, No. 339,049, No. 4,760,01 3, No. 4,734,4 No. 4, 2,833,827, German Patent No. 2,904, 626 Patent, the 3,604,580 Patent, 3, 604, 581 No. sulfonium salts described in the specification of, J. V. Crivelloetal, Macromolecules, 10 (6), 1307 (1977), J. Org. V. Crivelloetal, J.A. PolymerSci. , Polymer Chem. Ed. , Selenonium salts described in C., 17, 1047 (1979); S. Wenetal, Teh, Proc. Conf. Rad. Curing ASIA, p 478 Tokyo, Oct (1988), and onium salts such as arsonium salts.
In particular, from the viewpoint of reactivity and stability, the acid generator is preferably the above-mentioned oxime ester compound or onium salt compound.
Preferred examples of the onium salt compound include diazonium salts, iodonium salts and sulfonium salts.
Based on the total solid content mass of the positive type radiation sensitive resin composition of the present invention, 0.. The content is preferably 01% by mass or more and 30% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less, and still more preferably 0.1% by mass or more and 15% by mass or less.
<Antioxidant>
Examples of the antioxidant include phenolic antioxidants, sulfur-based antioxidants, amine-based antioxidants and the like, and phenolic antioxidants are particularly preferable. The antioxidants can be used alone or in combination of two or more. The content of the antioxidant is preferably 0.1 parts by mass to 10 parts by mass with respect to a total of 100 parts by mass of the [A] polymer component contained in the positive-working radiation-sensitive resin composition of the present embodiment, Particularly preferably, it is 0.2 parts by mass to 5 parts by mass. By using in this range, the heat resistance of the infrared shielding film formed from the positive radiation sensitive resin composition can be further enhanced.
As an antioxidant, the antioxidant as described in Unexamined-Japanese-Patent No. 2011-227106 etc. can be used.
The multifunctional acrylate is 100 parts by mass or less, preferably 0.1 parts by mass to 80 parts by mass, and more preferably 0.5 parts by mass to 50 parts by mass with respect to 100 parts by mass of the polymer component [A]. 1 part by weight or more and 25 parts by weight or less is more preferable. By using it in this range, the heat resistance and solvent resistance of the infrared shielding film formed from the positive radiation sensitive resin composition can be further enhanced.
As polyfunctional acrylate, polyfunctional acrylate described in JP-A-2005-227525 or the like can be used.

  A surfactant is a component which improves the film-formability of the said positive radiation sensitive resin composition. The said positive radiation sensitive resin composition can improve the surface smoothness of a coating film by containing surfactant, As a result, the infrared shielding film formed from the said positive radiation sensitive resin composition The film thickness uniformity can be further improved.

  The adhesion aiding agent is a component that improves the adhesion between the film forming object such as a substrate and the infrared shielding film. The adhesion promoter is particularly useful for improving the adhesion between the inorganic substrate and the infrared shielding film.

As a close_contact | adherence adjuvant, a functional silane coupling agent is preferable.
Inorganic oxide particles that are oxides containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium and hafnium as the inorganic oxide particles Can be used. The inorganic oxide particles described in JP-A-2011-128385 can be used.
<Compound Having Cyclic Ether Group>
The compound which has a cyclic ether group is a compound which has a cyclic ether group and is different from the polymer which a [A] polymer component has. The positive type radiation sensitive resin composition contains a compound having a cyclic ether group, thereby promoting the crosslinking of the polymer component [A] and the like by the thermal reactivity of the compound having a cyclic ether group, and the positive type While being able to raise the hardness of the infrared rays shielding film formed from a radiation sensitive resin composition more, the radiation sensitivity of the said positive radiation sensitive resin composition can be raised.

  The compound having a cyclic ether group is preferably a compound having two or more epoxy groups (oxiranyl group, oxetanyl group) in the molecule. As a compound which has an epoxy group as a compound which has a cyclic ether group, the compound of Unexamined-Japanese-Patent No. 2011-257537 can be used.

  Among these, as a compound having a cyclic ether group, a compound having two or more oxetanyl groups in the molecule is preferable, and bis [(3-ethyl oxetan-3-yl) methyl] isophthalic acid, 1,4- Bis [(3-ethyloxetan-3-yl) methoxymethyl] benzene, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (EHPE 3150 ( Daicel Chemical Co., Ltd.) is more preferable.

The content of the compound having a cyclic ether group is usually 150 parts by mass or less, preferably 0.5 parts by mass or more and 100 parts by mass or less, and 1 part by mass or more with respect to 100 parts by mass of the polymer component [A]. 50 parts by mass or less is more preferable, and 10 parts by mass or more and 25 parts by mass or less are more preferable. By making content of the compound which has cyclic ether group into the said range, the hardness of the infrared rays shielding film formed from the said positive radiation sensitive resin composition can be raised more.
<Method of Preparing Positive-Type Radiation-Sensitive Resin Composition>
The positive type radiation sensitive resin composition is dissolved or mixed by mixing a [A] polymer, a [B] quinone diazide compound, a [C] infrared shielding material, a suitable component as necessary, and other optional components in a solvent. It is prepared in the dispersed state. For example, the said positive radiation sensitive resin composition can be prepared by mixing each component in a solvent by a predetermined | prescribed ratio.
<Solvent>
As the solvent, one which dissolves or disperses the other components in the positive type radiation sensitive resin composition uniformly and does not react with the other components is suitably used. As such solvent, for example, alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether propionate, Aromatic hydrocarbons, ketones, other esters and the like can be mentioned. As a solvent, the solvent of Unexamined-Japanese-Patent No. 2011-232632 can be used.
<Polymer composition>
The polymer composition of the present invention comprises a polymer having a first structural unit containing an acid dissociable group, a second structural unit containing a crosslinkable group, and at least one selected from the group consisting of other structural units. Contains ingredients. This polymer component is the same as the [A] polymer component of the positive type radiation sensitive resin composition.
<Infrared shielding film>
The infrared shielding film of the present invention is formed from the positive radiation sensitive resin composition. Since the said infrared rays shielding film is formed from the said positive type radiation sensitive resin composition, it has the outstanding water repellency, the external appearance characteristic of a coating film, and the uniformity of a film thickness. The infrared shielding film having such characteristics can be suitable as an infrared shielding film of a solid-state imaging device, an illuminance sensor, a proximity sensor, and the like. In addition, it does not specifically limit as a formation method of the said infrared rays shielding film, It is preferable to apply the formation method of the infrared rays shielding film demonstrated below.
<Method of forming infrared shielding film>
The said positive radiation sensitive resin composition can be used suitably for formation of an infrared rays shielding film.

  In the method of forming an infrared shielding film of the present invention, a step of forming a coating on a substrate using the positive radiation sensitive resin composition (hereinafter also referred to as “step (1)”), at least the above coating A step of partially irradiating radiation (hereinafter also referred to as “step (2)”), a step of developing a coating film irradiated with radiation (hereinafter also referred to as “step (3)”), and a developed coating It has a step of heating the film (hereinafter also referred to as "step (4)").

According to the formation method of the said infrared rays shielding film, the infrared rays shielding film whose stability of pattern shape is high can be formed. Moreover, since the film thickness change amount of the unexposed area can be suppressed, as a result, the production process margin can be improved, and the improvement of the yield can be achieved. Furthermore, an infrared shielding film having a fine and elaborate pattern can be easily formed by forming a pattern by exposure, development, and heating utilizing photosensitivity.
[Step (1)]
In this step, the positive radiation sensitive resin composition is applied onto a substrate to form a coating film. When the said positive radiation sensitive resin composition contains a solvent, it is preferable to remove a solvent by prebaking a coating surface.

Examples of the substrate include glass, quartz, silicone, resin and the like. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, a ring-opened polymer of cyclic olefin, and a hydrogenated product thereof. The conditions for pre-baking may differ depending on the type of each component, the mixing ratio, and the like, but are usually 70 ° C. to 120 ° C. and about 1 minute to 10 minutes.
[Step (2)]
In this step, at least a part of the coating film is exposed to radiation by radiation. At the time of exposure, exposure is usually performed through a photomask having a predetermined pattern. As radiation used for exposure, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is more preferable. The exposure amount ^is preferably ^{500J / m 2 ~6,000J / m 2} , 1,500J / m 2 ~1,800J / m 2 is more preferable. The exposure dose is a value obtained by measuring the intensity of radiation at a wavelength of 365 nm using a luminometer ("OAI model 356" by OAI Optical Associates).
[Step (3)]
In this process, the coating film irradiated with radiation is developed. By developing the coating film after exposure, unnecessary portions (irradiated portions) are removed to form a predetermined pattern.

As a developing solution used at this process, alkaline aqueous solution is preferable. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia; and quaternary ammonium salts such as tetramethyl ammonium hydroxide and tetraethyl ammonium hydroxide. Be
Moreover, as a developing solution containing an organic solvent, organic solvents, such as a ketone system organic solvent and alcohol system organic solvent, can also be used. By using a developer containing such an organic solvent, a pattern in which the negative and positive are reversed can be formed (see, for example, JP-A-2014-199272).

  An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous alkali solution. The concentration of alkali in the aqueous alkali solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of obtaining suitable developability.

  Examples of the development method include a liquid deposition method, a dipping method, a rocking immersion method, a shower method and the like. As development time, although it changes with compositions of the said positive radiation sensitive resin composition, it is about 10 to 180 second normally.

  Following such development processing, for example, after washing for 30 seconds to 90 seconds in running water, a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

It is preferable that the film thickness change rate of the film thickness after development with respect to the film thickness of the coating film before development is 90% or more. As described above, according to the formation method using the positive-working radiation-sensitive resin composition, the amount of change in film thickness of the unexposed area with respect to development time can be suppressed, and the film thickness after development is the film thickness before development. Can maintain 90% or more of
[Step (4)]
In this step, the developed coating is heated. By heating the patterned thin film using a heating device such as a hot plate or an oven, the curing reaction of the polymer component [A] can be promoted to form an infrared shielding film. As heating temperature, it is about 120 degreeC-250 degreeC, for example. As a heating time, although it changes with kinds of heating apparatus, it is about 5 minutes-30 minutes in a hot plate, for example, and about 30 minutes-90 minutes in oven. In addition, a step baking method or the like in which two or more heating steps are performed can also be used. In this way, a patterned thin film corresponding to the desired infrared shielding film can be formed on the surface of the substrate. The thickness of the infrared shielding film is preferably 0.1 μm to 8 μm, and more preferably 0.1 μm to 6 μm.
<Solid-state imaging device>
FIG. 1 is a schematic cross-sectional view showing the configuration of a camera module provided with a solid-state imaging device.

  The camera module 200 shown in FIG. 1 is connected to a circuit board 70 which is a mounting board via a solder ball 60 which is a connecting member.

  In detail, the camera module 200 is provided on the first principal surface side (light receiving side) of the solid-state imaging element substrate 100 having the imaging element portion on the first principal surface of the silicon substrate and the solid-state imaging element substrate 100 A planarizing layer (not shown in FIG. 1, film under the layer 42), and a glass substrate 30 (light transmissive substrate) disposed above the infrared shielding film provided on the planarizing layer; A lens holder 50 disposed above the glass substrate 30 and having an imaging lens 40 in an internal space, and a light shielding and electromagnetic shield 44 disposed so as to surround the solid imaging element substrate 100 and the glass substrate 30 It is done. Each member is adhered by an adhesive (not shown in FIG. 1) 45.

  The present invention is a method of manufacturing a camera module having a solid-state imaging device substrate and an infrared shielding film disposed on the light-receiving side of the solid-state imaging device substrate, and the positive of the present invention is provided on the light-receiving side of the solid-state imaging device substrate. An infrared shielding film is formed by applying a mold radiation sensitive resin composition.

  Therefore, in the camera module according to the present embodiment, for example, the infrared radiation shielding film is formed by applying the positive type radiation sensitive resin composition of the present invention on the flattening layer. The method of forming the infrared shielding film is as described above.

  In the camera module 200, incident light hv from the outside passes through the imaging lens 40, the glass substrate 30, the near-infrared cut filter 42, and the flattening layer 46 sequentially, and then reaches the imaging element portion of the solid-state imaging element substrate 100 It has become.

Further, the camera module 200 is connected to the circuit board 70 on the second principal surface side of the solid-state imaging element substrate 100 via the solder balls 60 (connection material).
<Illumination sensor>
The configuration of the illuminance sensor according to the present embodiment will be described with reference to FIG. FIG. 2 is a cross-sectional view showing the configuration of the illuminance sensor. As shown in this figure, the illuminance sensor includes a glass epoxy resin substrate 4, an illuminance sensor light receiving element 6, a distance detecting light receiving element 8, an infrared light emitting element 10, a gold wire 12, a visible light resin 14, an infrared cut resin 16, and An infrared shielding film 18 is provided. In the illuminance sensor 1, the infrared light emitted from the infrared light emitting element 10 and reflected by the object is incident on the distance detecting light receiving element 8 to detect the distance. The illuminance sensor unit 2 includes a glass epoxy resin substrate 4, an illuminance sensor light receiving element 6, a gold wire 12, a visible light resin 14, a resin 16, and an infrared shielding film 18.

EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In addition, the weight average molecular weight (Mw) of the [A] polymer component was measured by the following method.
[Weight average molecular weight (Mw)]
It measured by gel permeation chromatography (GPC) under the following conditions.

Device: Showa Denko "GPC-101"
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 combined Mobile phase: tetrahydrofuran Column temperature: 40 ° C
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard substance: Monodispersed polystyrene <Synthesis of [A] polymer component>
Synthesis Example 1 Synthesis of Polymer (A-1)
In a flask equipped with a condenser and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were charged. Subsequently, 13 parts by mass of methacrylic acid, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of α-methyl-p-hydroxystyrene, 10 parts by mass of styrene, 12 parts by mass of tetrahydrofurfuryl methacrylate, 15 parts by mass of N-cyclohexylmaleimide and n- 10 parts by mass of lauryl methacrylate was charged, and after substitution with nitrogen, the temperature of the solution was raised to 70 ° C. while stirring gently, and this temperature was maintained for 5 hours to polymerize polymer (A-1). The solution contained was obtained. Mw of the polymer (A-1) was 8,000.
Synthesis Example 2 Synthesis of Polymer (A-2)
Under dry nitrogen gas, 29.30 g (0.08 mol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane (Central Glass Co., Ltd.), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 1 .24 g (0.005 mol), 3.27 g (0.03 mol) of 3-aminophenol (Tokyo Chemical Industry Co., Ltd.) as an end capping agent with N-methyl-2-pyrrolidone (hereinafter referred to as NMP) It was dissolved in 80 g. To this was added 31.2 g (0.1 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride (Manac) together with 20 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours I did. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotroping water with xylene. After completion of the stirring, the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours to obtain a polymer (A-2) having a structure represented by the following formula.

Synthesis Example 3 Synthesis of Polymer (A-3)
In a container equipped with a stirrer, 20 parts by mass of propylene glycol monomethyl ether was charged. Subsequently, 50 parts by mass of methyltrimethoxysilane, 30 parts by mass of phenyltrimethoxysilane, and 20 parts by mass of γ-glycidoxypropyltrimethoxysilane were charged, and the solution was heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.15 parts by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were charged, heated to 75 ° C., and held for 4 hours. Furthermore, the solution temperature was brought to 40 ° C., and evaporation was carried out while maintaining this temperature to remove ion-exchanged water and methanol generated by hydrolysis condensation. By the above, a polymer (A-3) was obtained as polysiloxane which is a hydrolysis condensation product. Mw of the polymer (A-3) which is a polysiloxane was 5,000.
Synthesis Example of Phosphate Ester Copper Complex
Pyridine solution (180 mL Wako Pure Chemical Industries, Ltd.) of 50 g of 2-hydroxyethyl methacrylate (0.38 mol, Wako Pure Chemical Industries, Ltd.), 73.6 g of phenyl phosphate (0.42 mol, Tokyo Chemical Industry Co., Ltd.) A pyridine solution (400 mL) of 116 g of 1,3,5-triisopropylsulfonic acid chloride (0.38 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the above at a temperature of 5 ° C. or less. After the addition, the reaction was terminated by stirring at room temperature for 6 hours. The mixture was washed with ethyl acetate after adding 2.9 L of a 10% aqueous sodium hydrogen carbonate solution so that the temperature did not rise above 30 ° C. The aqueous layer was adjusted to pH 1 by the addition of concentrated hydrochloric acid and the target substance was extracted with ethyl acetate. After distilling off the solvent, chloroform / water solution was carried out to remove 1,3,5-triisopropylsulfonic acid which was by-produced during the reaction. Finally, 10 mg of paramethoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the solvent of the organic layer was distilled off to obtain a phosphate compound (22 g, yield 20%).

The phosphoric acid ester (3.15 g, 11.0 mmol) and methanol (16.6 g) were mixed to prepare a methanol solution of phosphoric acid ester. Copper acetate (1 g, 5.5 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) was added to a methanol solution of the phosphate ester, and the temperature was raised to 50 ° C., and reaction was performed for 2 hours. After completion of the reaction, acetic acid and the solvent generated were distilled off with an evaporator to obtain phosphate ester copper complex 1 (3.5 g).
[Preparation of positive-working radiation-sensitive resin composition]
The [B] quinone diazide compound, the [C] infrared ray shielding material, and other optional compounds used for preparation of the positive type radiation sensitive resin composition are shown below.
([A] polymer)
A-1: The polymer (A-1) obtained in Synthesis Example 1
A-2: Polymer obtained in Synthesis Example 2 (A-2)
A-3: The polymer (A-3) obtained in Synthesis Example 3
A-4: Novolak resin (trade name, XPS-4958G, m-cresol / p-cresol ratio = 55/45 (weight ratio), Gunei Chemical Industry Co., Ltd.)
([B] quinone diazide compound)
B-1: 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid chloride Condensate B-2: Condensate of 1,1,1-tri (p-hydroxyphenyl) ethane and 1,2-naphthoquinonediazide-5-sulfonic acid chloride ([C] infrared shielding material)
C-1: YMF-02 (18.5 mass% dispersion of cesium tungsten oxide (Cs _0.33 WO ₃ (average dispersed particle size 800 nm or less) manufactured by Sumitomo Metal Mining Co., Ltd.)
C-2: Cyanine dye (Daito Chemix Daito chmix 1371F, maximum absorption wavelength (λ max = 805 nm)
C-3: Phosphate ester copper complex 1 obtained by the synthesis of the above phosphate ester copper complex
(Compound having [D] cyclic ether group)
D-1: Isophthalic acid bis [(3-ethyl oxetan-3-yl) methyl] represented by the following formula (D-1)
D-2: 1,4-bis [(3-ethyloxetan-3-yl) methoxymethyl] benzene represented by the following formula (D-2)

([F] antioxidant)
F-1: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] ("Adekastab AO-60" from Adeka)
[Preparation of Positive Radiation-Sensitive Resin Composition 1]
[A] A polymer solution containing (A-1) as a polymer component (an amount corresponding to 100 parts by mass (solid content) of polymer (A-1)), [B] quinone diazide compound (B-1) 25 parts by mass, 18 parts by mass of (C-1) as a [C] infrared shielding material, 5 parts by mass of (D-1) as a compound having a [D] cyclic ether group, and as an [F] antioxidant (F-1) 0.5 parts by mass was mixed to prepare a positive type radiation sensitive resin composition 1 (hereinafter also referred to as "composition 1").
[Preparation of Positive Radiation-Sensitive Resin Composition 2]
[A] A polymer solution containing (A-2) as a polymer component (an amount corresponding to 100 parts by mass (solid content) of the polymer (A-2)), (B- as a [B] quinone diazide compound 2) 30 parts by mass, 30 parts by mass of (C-2) as a [C] infrared shielding material, and 5 parts by mass of (D-2) as a compound having a [D] cyclic ether group; Resin composition 2 (hereinafter also referred to as “composition 2”) was prepared.
[Preparation of Positive Radiation-Sensitive Resin Composition 3]
[A] A polymer solution containing a polymer (A-3) as a polymer component (an amount corresponding to 100 parts by mass of the polymer (A-3) (each solid content)) as a [B] quinone diazide compound (B-1) 25 parts by mass, [C] 20 parts by mass as an infrared shielding material, and 1 part by mass of (F-1) as an antioxidant are mixed to form a positive-working radiation-sensitive resin composition An article 3 (hereinafter also referred to as “composition 3”) was prepared.
[Preparation of Positive Radiation-Sensitive Resin Composition 4]
[A] 35 parts by mass of (B-1) as a [B] quinonediazide compound, and (C-3) 20 as a [C] infrared shielding material, in 100 parts by mass of the polymer (A-4) as a polymer component The mass part and 1 mass part of (F-1) as antioxidant were mixed, and positive type radiation sensitive resin composition 4 (it is also called the "composition 4" hereafter) was prepared.

  In the comparative example, in preparation of the positive type radiation sensitive resin composition 1, except not containing the (C-1) compound, it adjusted similarly (it is also called the following "comparative composition 1").

<Evaluation>
The radiation sensitivity, the infrared shielding property, and the chemical resistance of the infrared shielding film were evaluated using the positive type radiation sensitive resin compositions 1 to 4 and the positive type radiation sensitive resin composition of the comparative example.
Example 5 evaluated similarly except having used butyl acetate for the developing solution using positive type radiation sensitive resin composition 1. As shown in FIG. In Example 5, the unexposed area is developed with butyl acetate to obtain a pattern in the exposed area. The evaluation results are shown in Table 1.
[Evaluation of radiation sensitivity]
The positive type radiation sensitive resin composition was applied on a silicon substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 25.0 μm. Then, it exposes through a photomask which has a square island pattern of 200 micrometers using an exposure machine ("MPA-600FA" (Ghi line mixing) of Canon Inc.), and changes the exposure amount to radiation with respect to the coating film Irradiated. Thereafter, it was developed by immersion in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23.degree. C. for 80 seconds. Subsequently, the pattern was formed by performing flowing-water washing | cleaning with ultrapure water for 1 minute, and drying after that. At this time, the exposure amount required to completely dissolve the 200 μm square island pattern was examined. When the value of the exposure dose is 300 mJ / cm ² or less, it can be judged that the radiation sensitivity is good.
Evaluation criteria are shown below.
A: Less than 300 mJ / cm ²
B: 300mJ / cm ² or more and less than 400mJ / cm ^2,
[Evaluation of infrared shielding properties]
After applying a positive type radiation sensitive resin composition to a glass substrate using a spinner under the above conditions, a photosensitive layer (curable composition layer) coating film having a thickness of 25 μm is formed, and a spectrophotometer (Hitachi, Ltd.) The transmittance of the coating film at a wavelength of 1200 nm was measured using "150-20 type double beam" manufactured by Tokuyama K.K. The lower the numerical value, the better the infrared shielding properties. It can be said that practically satisfactory infrared shielding properties are exhibited when the permeability is 2% or less.
[Evaluation of chemical resistance of infrared shielding film]
The chemical resistance of the infrared shielding film was evaluated as swelling by the stripping solution. The positive type radiation sensitive resin composition was coated on a silicon substrate using a spinner and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 25.0 μm. Then, it baked for 30 minutes using the oven heated at 230 degreeC, and formed the infrared rays shielding film. This film was immersed in an N-methylpyrrolidone solvent heated to 40 ° C. for 3 minutes, and the film thickness change rate (%) before and after the immersion was determined as an index of chemical resistance. The film thickness change rate is A: film thickness change rate less than 5%, B: film thickness change rate 5% or more and less than 10%, C: film thickness change rate 10% or more and less than 15%. The drugability was evaluated as good. The film thickness was measured at 25 ° C. using an optical interference film thickness measuring apparatus (Lambda Ace VM-1010).
[Evaluation of refractive index (photorefractive)]
The refractive index of the substrate having the infrared shielding film formed in the chemical resistance evaluation was measured by Metricon's “prism coupler model 2010”. The refractive index was measured at three wavelengths of 408 nm, 633 nm and 828 nm. The refractive index was evaluated as “A” when the measured value at 633 nm was 1.60 or more as “B” when it was less than 1.600. When the refractive index is high, it can be said that it is good from the viewpoint of optical characteristics.

As is clear from the results in Table 1, the positive type radiation sensitive resin compositions of Examples 1 to 4 were excellent in radiation sensitivity, and excellent in infrared shielding properties, chemical resistance, and refractive index.
On the other hand, it was found that the positive type radiation sensitive resin composition of the comparative example is inferior to the infrared ray shielding property and the refractive index of those having excellent radiation sensitivity and chemical resistance.

30 glass substrates,
40 imaging lenses,
42 infrared shielding film,
44 Shielding and electromagnetic shielding,
45 glue,
50 lens holders,
60 solder balls,
70 circuit boards,
100 solid-state imaging element substrate 200 camera module 1 illuminance sensor 2 illuminance sensor unit 4 glass epoxy resin substrate (substrate)
6 illuminance sensor light receiving element 8 light receiving element for distance detection 10 infrared light emitting element (light emitting element)
12 gold wire 14 visible light resin (first visible light resin second visible light resin)
16 Visible light and infrared cut resin 18 Infrared shielding film

Claims (10)

[A] alkali soluble resin,
A positive radiation-sensitive resin composition comprising the [B] quinonediazide compound, and the [C] infrared shielding material ,
The [C] infrared shielding material is selected from cesium oxide tungsten, copper compounds, cyanine dyes, phthalocyanine dyes, quaterylene dyes, aminium dyes, iminium dyes, ami dyes, azo dyes, anthraquinone dyes, diimonium dyes, squarylium dyes, porphyrin dyes A positive radiation-sensitive resin composition containing at least one of The positive radiation-sensitive resin according to claim 1, wherein the alkali-soluble resin (A) is at least one polymer selected from an acrylic resin having a carboxyl group, a polyamic acid, a polyimide resin, a polysiloxane and a novolac resin. Resin composition. The positive type radiation sensitive resin composition according to claim 1 or 2, wherein the copper compound is a phosphorus-containing compound . The content of the said cesium tungsten oxide is 5 mass% or more and 70 mass% or less with respect to the total solid mass of the said radiation sensitive resin composition, The claim 1 or any one of Claim 3 Positive radiation sensitive resin composition as described. The radiation sensitive resin is at least one selected from the copper compound, cyanine dye, phthalocyanine dye, quaterylene dye, aminium dye, iminium dye, ami dye, azo dye, anthraquinone dye, diimonium dye, squarylium dye, porphyrin dye The positive type radiation sensitive resin composition according to any one of claims 1 to 4, which is 1% by mass or more and 30% by mass or less with respect to the total solid content mass of the composition.  The infrared rays shielding film formed using the positive type radiation sensitive resin composition as described in any one of Claims 1-5. A solid-state imaging device having the infrared shielding film according to claim 6 . An illuminance sensor having the infrared shielding film according to claim 6 . (1) A step of forming a coating film of the positive type radiation sensitive resin composition according to any one of claims 1 to 5 on a substrate,
(2) irradiating at least a part of the coating film formed in the step (1) with radiation;
(3) a step of developing the coating film irradiated with radiation in the step (2), and (4) a step of heating the coating film developed in the step (3). Method. The method according to claim 9 , wherein a developer containing an organic solvent is used in the step (2).