TWI572981B - Composition for solder resist, cured membrane and method for manufacturing the cured film - Google Patents

Description

Solder resist composition, cured film, and cured film manufacturing method

This invention relates to a solder resist composition. Further, the present invention relates to a cured film using a solder resist composition and a method of producing the cured film. Further, the present invention relates to a solid-state imaging device including the cured film, a liquid crystal display device, or an organic electroluminescence (EL) display device.

Previously, in the case of forming a permanent pattern of a solder resist or the like, when a photosensitive layer is to be formed on a target member, the following method is used: a liquid composition by a spin coating method, a screen printing method, or a spray printing method a method of forming a film as a coating film and drying it; applying a composition to a temporary support and drying to form a laminated film having a photosensitive layer, and then using a vacuum laminator or a roll laminator A method of transferring a photosensitive layer onto a member. As a method of forming a permanent pattern such as a solder resist or the like, for example, a method of forming a permanent pattern on a germanium wafer, a wired germanium wafer, or a copper clad laminate, or the like is known. The photosensitive layer is formed by the above method, and the photosensitive layer in the laminated body is exposed, and after exposure, the photosensitive layer is developed to form a pattern, and then subjected to a curing treatment or the like to form a permanent pattern. case.

The permanent pattern of such a solder resist is widely used for a solid-state imaging device (image sensor) used in a mobile phone, a digital camera, a digital camera, a surveillance camera, etc. (Japanese Patent Laid-Open Publication No. 2012-003225).

However, the solder resist composition is not used for pattern formation immediately after preparation, and is often used for pattern formation after being temporarily stored. The inventors of the present application have studied various performances after storage for a certain period of time, and as a result, it has been found that various performances tend to deteriorate. An object of the present invention is to solve the problem, and an object of the invention is to provide a solder resist composition which is excellent in infrared light shielding property and which has little deterioration over time.

In the above-mentioned problem, the inventors of the present invention conducted an effort to find a solder resist composition which is excellent in infrared light-shielding property and has little deterioration after time by using a specific polymerizable compound. In particular, as shown in the examples described later, even a compound similar to the specific polymerizable compound used in the present invention has a large difference in deterioration after the passage, and thus the effect of the present invention is known. How amazing it is.

Specifically, the above problem is solved by the following means <1>, preferably by means <2> to <20>.

<1> A solder resist composition comprising the compound represented by the formula (1) and infrared light-blocking particles.

General formula (1)

In the formula (1), L is a group each containing a combination of an alkylene group and -O-, and each of Ac is a (meth)acryloxy group.

<2> The solder resist composition according to <1>, wherein, in the formula (1), L is a group including a combination of -CH ₂ - and -O-.

<3> The solder resist composition according to <1>, wherein the infrared ray blocking particles comprise a tungsten compound.

<4> The solder resist composition according to <1>, wherein the infrared light-shielding particles are represented by the following general formula (2).

M _x W _y O _z (2); M represents a metal, W represents tungsten, O represents oxygen; 0.001 ≦ x / y ≦ 1.1; 2.2 ≦ z / y ≦ 3.0.

<5> The solder resist composition according to <4>, wherein in the formula (2), M is an alkali metal.

<6> The solder resist composition according to <4>, wherein in the formula (2), M is ruthenium.

The solder resist composition according to any one of <1> to <6> wherein, in the formula (1), L is a group comprising a combination of -C ₂ H ₄ - and -O-.

<8> A solder resist composition according to any one of <1> to <7> Further, it further comprises a polymerization initiator.

The solder resist composition according to any one of <1> to <7> which further comprises an α-amino ketone polymerization initiator.

<10> The solder resist composition according to any one of <1> to <9> which further comprises an alkali-soluble binder.

The solder resist composition according to any one of <1> to <10> wherein the solid content concentration is 30% by mass to 80% by mass.

<12> A cured film formed by curing the solder resist composition according to any one of <1> to <11>.

<13> A solid-state image sensor, a liquid crystal display device, or an organic EL display device, comprising the cured film according to <12>.

<14> A method of producing a pattern-hardening film, comprising: applying a solder resist composition according to any one of <1> to <11> to a substrate; and patterning the solder resist composition The steps of exposure.

<15> A solid-state imaging device, a liquid crystal display device, or a method of manufacturing an organic EL display device, comprising: the step of applying the solder resist composition according to any one of <1> to <11> to a substrate; And a step of exposing the above solder resist composition.

The solder resist composition according to any one of <1> to <11>, further comprising a solvent, an alkali-soluble resin (preferably 30% by mass to 80% by mass of the total solid content), and polymerization Starting agent, surfactant, sensitizer, ultraviolet absorber, decane coupling agent, filler (preferably 1% to 60% by mass of total solid content) And at least one of the dispersing agents.

The solder resist composition according to any one of <1> to <11>, further comprising a solvent, an alkali-soluble resin, and a polymerization initiator.

The solder resist composition according to any one of <1>, wherein the film has a transmittance of 2 at a wavelength of 1200 nm when the film thickness is changed to 25 μm. %the following.

<19> The solder resist composition according to any one of <1> to <11>, wherein the viscosity at 25 ° C is 10 mPa. s~3000mPa. s.

<19> A time-dependent deterioration agent for a solder resist composition, which is represented by the formula (1).

In the formula (1), L is a group containing a combination of an alkylene group and -O-, and Ac is a (meth)acryloxy group.

A solder resist composition which is excellent in infrared light shielding property and has little deterioration after time can be provided.

2‧‧‧ Large pattern

3‧‧‧Micropattern

10‧‧‧矽 substrate

12‧‧‧Photographic components

13‧‧‧Interlayer insulating film

14‧‧‧ base layer

15R‧‧‧Red color filter

15G‧‧‧Green color filter

15B‧‧‧Blue color filter

16‧‧‧Protective layer

17‧‧‧Microlens

18‧‧‧Shade film

20‧‧‧Adhesive

22‧‧‧Insulation film

23‧‧‧Metal electrodes

24‧‧‧ solder resist layer

26‧‧‧Internal electrodes

27‧‧‧Component surface electrode

30‧‧‧ glass substrate

40‧‧‧ imaging lens

41‧‧‧Adhesive

42‧‧‧Infrared cut filter

43‧‧‧Adhesive

44‧‧‧Lighting and electromagnetic shielding

45‧‧‧Adhesive

50‧‧‧ lens holder

60‧‧‧ solder balls

70‧‧‧ circuit board

100‧‧‧Solid imaging element substrate

200‧‧‧ camera module

300‧‧‧矽 substrate

310‧‧‧Circular metal electrode

320‧‧‧Shade film

330‧‧‧resist layer

340‧‧‧Shade film

410‧‧‧Substrate

412, 420‧‧ lens

412a‧‧‧ lens surface

412b‧‧‧ lens edge

414‧‧‧Shade film

414A‧‧‧Shutter coating layer

414a‧‧‧ lens opening

450‧‧‧Distributor

460, 480‧‧‧ mold

462, 482 ‧ ‧ recess

470‧‧‧ mask

Hν‧‧‧Into the light

M‧‧‧ molding materials

1 is a view showing a camera including a solid-state imaging element according to an embodiment of the present invention; A schematic cross-sectional view of the configuration of the module.

Fig. 2 is a schematic cross-sectional view showing a solid-state image sensor according to an embodiment of the present invention.

3 is a schematic cross-sectional view of a substrate A used in Example 2-1 and Example 2-2.

4 is a schematic cross-sectional view showing a state in which a light shielding film is formed on a substrate A.

Fig. 5 is a schematic cross-sectional view showing a substrate B used in Example 2-1 and Example 2-2.

FIG. 6 is a schematic cross-sectional view showing a state in which a light shielding film is formed on a substrate B.

Fig. 7 is a plan view showing an example of a wafer level lens array.

Figure 8 is a cross-sectional view taken along line A-A of Figure 7.

FIG. 9 is a view showing a state in which a molding material serving as a lens is supplied onto a substrate.

10A to 10C are views showing a procedure of molding a lens on a substrate by a mold.

11A to 11C are schematic views showing a procedure of forming a pattern-shaped light-shielding film on a substrate on which a lens is formed.

Fig. 12 is a cross-sectional view showing an example of a wafer level lens array.

13A to 13C are schematic views showing other aspects of the light shielding film forming step.

14A to 14C are schematic views showing a procedure of molding a lens on a substrate having a patterned light shielding film.

Fig. 15 is a diagram of a pattern in exposure used in the embodiment.

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

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

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

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

The infrared ray in the present invention means an electromagnetic wave having a wavelength of from 700 nm to 2,500 nm.

The solder resist composition of the present invention (hereinafter sometimes referred to as "the composition of the present invention"), a cured film, a solid-state imaging device, a liquid crystal display device, an organic EL display device, a method for producing a patterned cured film, a solid-state imaging device, Liquid crystal display device or The method of manufacturing the organic EL display device will be described in detail. The description of the constituent elements described below may be performed based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

The solder resist composition of the present invention is characterized by comprising a compound represented by the formula (1) and infrared light-blocking particles.

<Compound represented by the general formula (1)>

The composition of the present invention includes a compound represented by the general formula (1).

In the formula (1), L is a group each containing a combination of an alkylene group and -O-, and each of Ac is a (meth)acryloxy group.

In the formula (1), L is preferably a group each comprising a combination of -CH ₂ - and -O-, more preferably a group comprising a combination of -C ₂ H ₄ - and -O-, and more preferably a group in which -C ₂ H ₄ - is alternately repeated with -O-. In this case, the group bonded to L and the group bonded to Ac are preferably both -C ₂ H ₄ -. Further, the number of -C ₂ H ₄ - in L is preferably from 1 to 4, more preferably from 2 or 3.

In the general formula (1), the number of atoms constituting the main chain of L (the number of atoms of the chain between the Ac atom and the O atom) is preferably from 3 to 12, more preferably from 4 to 10. Further, for example, when the L moiety is -C ₂ H ₄ -OC ₂ H ₄ -, the number of atoms constituting the main chain of L is 5.

In the formula (1), it is preferred that four L's are the same.

Ac is more preferably an acryloxy group.

The molecular weight of the compound represented by the formula (1) is preferably from 400 to 1,100, more preferably from 600 to 1,000.

The viscosity of the compound represented by the general formula (1) is preferably 100 mPa. s~900mPa. s, more preferably 200mPa. s~500mPa. s.

It is preferable that all the components other than the solvent of the composition of the present invention contain the compound represented by the formula (1) in a ratio of from 1% by mass to 30% by mass, more preferably from 5% by mass to 15% by mass. The ratio of % contains the compound represented by the general formula (1). The compound represented by the formula (1) may be used alone or in combination of two or more. In the case of two or more types, it is preferred that the total amount thereof is within the above range.

Preferred examples of the compound represented by the formula (1) used in the present invention are shown below, but the present invention is of course not limited to these examples.

As an example of the above-mentioned compound, M-460 manufactured by Toagosei Co., Ltd., etc. can be illustrated.

The composition of the present invention may contain a polymerizable compound other than the compound represented by the above formula (1).

As another polymerizable compound, specifically, it has at least one, It is preferably selected from compounds having two or more terminal ethylenically unsaturated bonds. Such a compound group is widely known in the industrial field, and these compounds can be used without particular limitation in the present invention. These compounds may be, for example, any of the chemical forms such as monomers, prepolymers, i.e., dimers, trimers, and oligomers, or mixtures thereof, and multimers thereof. The polymerizable compound in the invention may be used alone or in combination of two or more.

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

As the specific compound, these can also be suitably used in the present invention. The compound described in Paragraph No. 0095 to Paragraph No. 0108 of Japanese Laid-Open Patent Publication No. 2009-288705.

Further, as the polymerizable compound, the polymerizable monomer is preferably a compound having at least one vinyl group capable of undergoing addition polymerization and having a boiling point of 100 ° C or higher at normal pressure. Base compound. Examples thereof include monofunctional acrylates or methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate. Polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol IV (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tri (propylene oxypropyl propyl) (meth)acrylic acid after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol, such as ether, tris(propylene methoxyethyl) isomeric cyanurate, glycerin or trimethylolethane The esterification of the (meth)acrylic acid urethanes as described in the Japanese Patent Publication No. Sho-48-41708, the Japanese Patent Publication No. Sho. Japanese Patent Laid-Open No. 48-64183, Japanese Patent Publication No. Sho 49-43191, and Japanese Patent Publication No. Sho 52-30490 Polyester acrylates described as a reaction product of an epoxy resin and (meth) acrylic acid esters of polyfunctional epoxy acrylic acrylates or methacrylates, and a mixture of these.

Further, a polyfunctional compound obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group or an ethylenically unsaturated group such as glycidyl (meth)acrylate may be mentioned. (Meth) acrylate, etc.

In addition, as the other preferable polymerizable compound, an anthracene ring described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, and Japanese Patent No. 4364216, and the like can be used. A compound having a difunctional or higher ethylenic polymerizable group, a cardo resin.

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

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

R: , , , ,-OH,-CH ₃

T: -(CH ₂ ) _m -, -OCH ₂ -, -OCH ₂ CH ₂ -, -OCH ₂ CH ₂ CH ₂ , -OCH ₂ CH ₂ CH ₂ CH ₂ - -O(CO)-(CH ₂ ) _m -, -COO-(CH ₂ ) _m -, -OCH(CH ₃ )-CH ₂ -, -OCH ₂ CH(CH ₃ )-

Z:-O-,

In the above formula, n is 0 to 14, and m is 1 to 8. There are more than one molecule The R and T of each one may be the same or different.

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

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

Further, a compound described in the general formula (1) and the general formula (2) together with the specific examples thereof can also be used as a polymerizable compound, and the above compound is among the above polyfunctional alcohols, in the above-mentioned Japanese Patent Publication No. Hei 10-62986. A compound obtained by (meth)acrylation after addition of ethylene oxide or propylene oxide.

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

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

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

A preferred acid value of the polyfunctional monomer having an acid group is from 0.1 mg-KOH/g to 40 mg-KOH/g, particularly preferably from 5 mg-KOH/g to 30 mg-KOH/g. When the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are lowered. When the acid value of the polyfunctional monomer is too high, production or handling becomes difficult, photopolymerization performance is lowered, and surface smoothness of the pixel is hardened. Sex becomes less good. Therefore, when two or more kinds of polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is necessary to adjust so that the acid value of the entire polyfunctional monomer is in the above range.

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

As a polyfunctional single body having a caprolactone structure, as long as it is intramolecular The caprolactone structure is not particularly limited, and examples thereof include ε-caprolactone-modified polyfunctional (meth) acrylate by trimethylolethane and di-trimethylol. Polyols such as ethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin, trimethylol melamine, and (meth)acrylic acid and ε-caprolactone The ε-caprolactone obtained by esterification is modified with a polyfunctional (meth) acrylate. Among them, a polyfunctional mono-weight having a caprolactone structure represented by the following formula (1) is preferred.

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

In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents an integer of 1 or 2, and "*" represents a bond.

In the formula, R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bond.

For example, the DPCA-20 sold by Nippon Kayaku Co., Ltd. as a KAYARAD DPCA series (in the above formula (1) to formula (3), m) =1, the number of groups represented by the formula (2) = 2, the compound in which R ¹ is a hydrogen atom), and DPCA-30 (in the above formula (1) to formula (3), m=1, the formula ( 2) the number of the groups represented by the formula = 3, the compound in which R ¹ is a hydrogen atom), DPCA-60 (in the above formulas (1) to (3), m = 1, the group represented by the formula (2) The number = 6 and the compound in which R ¹ is a hydrogen atom), DPCA-120 (in the above formulas (1) to (3), m = 2, the amount of the group represented by the formula (2) = 6, R ¹ is a compound of a hydrogen atom) and the like.

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

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

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

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

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

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

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

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

The compound represented by the above formula (i) or (ii) may be used alone or in combination of two or more. In particular, it is preferred that in the general formula (ii), six Xs are in the form of an acrylonitrile group.

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

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

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

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

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

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

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

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

In the formula, R ¹ represents an alkyl group, R ² represents an n-valent aliphatic group which may contain an atom other than carbon, R ⁰ represents an alkyl group which is not H, and n represents 2 to 4.

Specific examples of the polyfunctional thiol compound represented by the above formula (I) include 1,4-bis(3-mercaptobutyloxy)butane having the following structural formula [Formula (II) )], 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H5H)-trione [formula (III)], And pentaerythritol tetrakis(3-mercaptobutyrate) [formula (IV)] and the like. These polyfunctional thiols may be used alone or in combination of two or more.

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

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

The other polymerizable compound in the composition of the present invention is preferably 80% by mass or less, more preferably 60% by mass or less, still more preferably 40% by mass or less, still more preferably 10% by mass or less, particularly preferably These other polymeric compounds are substantially absent. The substance is, for example, 5% by mass of the amount of all the polymerizable compounds. Next, it is preferably 2% by mass or less.

<Infrared opaque particles>

The infrared ray blocking particles used in the present invention are compounds which satisfy the absorbance (500 nm) / absorbance (900 nm) < 0.3. The infrared light-shielding particles are preferably excellent in light permeability for exposure. From the viewpoint of the above, other infrared light-shielding particles are preferably selected from the group consisting of infrared absorbing dyes and infrared absorbing inorganic pigments. The infrared light-shielding particles used in the present invention are preferably a tungsten compound (a compound containing tungsten).

The tungsten compound is an infrared light-shielding particle which has high absorption of infrared rays (light having a wavelength of about 800 nm to 1200 nm) (that is, high light-shielding property (shielding property) for infrared rays) and low absorption of visible light. Therefore, according to the composition of the present invention, by containing a tungsten compound, a pattern having high light-shielding property in the infrared region and high light transmittance in the visible light region can be formed.

Further, the tungsten compound has a small absorption of light shorter than the visible region used for exposure of a high pressure mercury lamp, KrF, ArF or the like for image formation. Therefore, an excellent pattern can be obtained by combining such a tungsten compound with a polymerization initiator, a polymerizable compound, and an alkali-soluble binder.

Examples of the tungsten compound include a tungsten oxide compound, a tungsten boride-based compound, and a tungsten sulfide-based compound, and more preferably a tungsten oxide-based compound represented by the following formula (2).

M _x W _y O _z (2); M represents a metal, W represents tungsten, O represents oxygen; 0.001 ≦ x / y ≦ 1.1; 2.2 ≦ z / y ≦ 3.0.

Examples of the metal of M include an alkali metal, an alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga. In, T1, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi are preferably alkali metals. The metal of M may be one type or two or more types.

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

When x/y is 0.001 or more, infrared rays can be sufficiently shielded, and by x/y being 1.1 or less, it is possible to more reliably prevent the formation of an impurity phase in the tungsten compound.

When z/y is 2.2 or more, the chemical stability of the material can be further improved, and by z/y being 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the tungsten oxide-based compound represented by the above formula (2) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 ,} etc., preferably Cs _0.33 WO ₃ or Rb _0.33 WO ₃ , more preferably Cs _0.33 WO ₃ .

The average particle diameter of the tungsten compound is preferably 800 nm or less, more preferably 400 nm or less, still more preferably 200 nm or less. Since the average particle diameter is in such a range, it is difficult for the tungsten fine particles to block visible light due to light scattering, so that the light transmittance in the visible light region can be made more reliable. In view of avoiding light scattering, the average particle diameter is preferably as small as possible, but the average particle diameter of the tungsten fine particles is usually 1 nm or more for reasons such as ease of handling during production.

Tungsten compound relative to the total solid component mass of the composition of the present invention The content is preferably 3% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 10% by mass or less.

Further, two or more kinds of tungsten compounds can be used.

The tungsten compound can be obtained as a commercially available product. When the tungsten compound is, for example, a tungsten oxide-based compound, the tungsten oxide-based compound can be obtained by heat-treating a tungsten compound in an inert gas atmosphere or a reducing gas atmosphere (refer to Japan). Patent No. 4096205).

Further, the tungsten oxide-based compound can be obtained, for example, as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

Examples of the infrared absorbing dye include metal complexes such as cyanine dye, phthalocyanine dye, naphthalocyanine dye, immonium dye, ammonium dye, quinolinium dye, pyrylpurine dye, and Ni complex dye. Pigment and the like.

A coloring matter which can be used as an infrared light-shielding particle can also be obtained as a commercial item. For example, the following commercial coloring matter can be suitably used.

S0345, S0389, S0450, S0253, S0322, S0585, S0402, S0337, S0391, S0094, S0325, S0260, S0229, S0447, S0378, S0306, S0484 manufactured by FEW Chemicals

ADS795WS, ADS805WS, ADS819WS, ADS820WS, ADS823WS, ADS830WS, ADS850WS, ADS845MC, ADS870MC, ADS880MC, ADS890MC, ADS920MC, ADS990MC, ADS805PI, ADSW805PP, ADS810CO, ADS813MT, ADS815EI, manufactured by American Dye Source, Inc. ADS816EI, ADS818HT, ADS819MT, ADS819MT, ADS821NH, ADS822MT, ADS838MT, ADS840MT, ADS905AM, ADS956BP, ADS1040P, ADS1040T, ADS1045P, ADS1040P, ADS1050P, ADS1065A, ADS1065P, ADS1100T, ADS1120F

YKR-4010, YKR-3030, YKR-3070, MIR-327, MIR-371, SIR-159, PA-1005, MIR-369, MIR-379, SIR-128, PA-1006 manufactured by Yamamoto Chemicals Co., Ltd. , YKR-2080, MIR-370, YKR-3040, YKR-3081, SIR-130, MIR-362, YKR-3080, SIR-132, PA-1001

NK-123, NK-124, NK-1144, NK-2204, NK-2268, NK-3027, NKX-113, NKX-1199, NK-2674, NK-3508, NKX-114 manufactured by Linyuan Biochemical Research Institute , NK-2545, NK-3555, NK-3509, NK-3519

Among these pigments, a phthalocyanine dye and a metal complex dye are preferred from the viewpoint of heat resistance.

These dyes may be used singly, but in order to exhibit good light-shielding properties at 800 nm to 1200 nm, two or more of these dyes may be used in combination for the purpose.

Examples of the infrared absorbing inorganic pigment which can be used as another infrared light-shielding material include zinc oxide, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate, and barite powder. Lead dan, iron oxide red, chrome yellow, zinc yellow (zinc yellow 1 species, zinc yellow 2 species), ultramarine blue, Prussian blue (potassium ferrocyanide) ), Zircon Grey, Yellow (Praseodymium yellow), chrome titan yellow, chrome green, malachite green, Victoria green, iron blue (not related to Prussian blue), vanadium zirconium blue, chromium Chrome tin pink, manganese red, salmon pink, etc., and further, as the black pigment, it may be selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti. And a metal oxide, a metal nitride or a mixture of one or more metal elements in the group consisting of Ag and the like.

As the black pigment, titanium dioxide black which is a black pigment containing titanium nitride is preferable in terms of good shielding properties in an infrared region having a wavelength of 800 nm to 1200 nm.

Titanium black can be obtained by a known method, and as a commercial product, for example, it can be manufactured by Ishihara Sangyo Co., Ltd., manufactured by Ako Chemical Co., Ltd., manufactured by Mitsubishi Materials Co., Ltd., and manufactured by Mitsubishi Materials. Titanium black manufactured by the company and manufactured by Mitsubishi Materials Electronics Co., Ltd.

The term "titanium black" refers to black particles having a titanium atom. It is preferably low-valent titanium oxide or titanium oxynitride. As the titanium black particles, particles which have been modified on the surface can be used as needed in order to improve dispersibility and suppress cohesiveness.

The surface modification method may be a method of coating a surface by one or more selected from the group consisting of cerium oxide, titanium oxide, cerium oxide, aluminum oxide, magnesium oxide, and zirconium oxide, and may also be a Japanese patent. The water-repellent substance shown in Paragraph No. [0010] to Paragraph No. [0027] of JP-A-2007-302836 is subjected to surface treatment.

As a method for producing titanium black, there is a method of reducing a mixture of titanium oxide and titanium metal in a reducing environment (Japan) JP-A-49-5432); a method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open Publication No. SHO 57-205322) A method of subjecting titanium dioxide or titanium hydroxide to high-temperature reduction in the presence of ammonia (Japanese Patent Laid-Open Publication No. SHO 60-65069, Japanese Patent Application Laid-Open No. SHO 61-201610), and a vanadium compound attached to titanium oxide or titanium hydroxide A method of performing high-temperature reduction in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610); however, it is not limited to these methods.

The particle diameter of the titanium black particles is not particularly limited, but is preferably from 3 nm to 2,000 nm, and more preferably from 10 nm to 500 nm from the viewpoint of dispersibility and coloring property.

The specific surface area of the titanium black is not particularly limited, but the water repellency after the surface treatment of the titanium black by the water repellency agent is a predetermined property, and is determined by a Brunauer-Emmett-Teller (BET) method. value is usually about ^{5m 2 / g ~ 150m 2 /} g, particularly preferably from about ^{20m 2 / g ~ 100m 2 /} g.

The average particle diameter of the inorganic pigment used as the other infrared light-shielding particles is preferably from 3 nm to 0.01 mm, and the average particle diameter is preferably 10 nm from the viewpoints of dispersibility, light-shielding property, and precipitation with time. ~1μm.

The infrared light-shielding particles may be used alone or in combination of two or more. It is preferable that all components other than the solvent of the composition of the present invention contain infrared light-shielding particles in a ratio of from 1% by mass to 30% by mass, and more preferably from 5% by mass to 15% by mass. Sex particles.

<Other ingredients>

The composition of the present invention may also contain a solvent, an alkali-soluble resin, and polymerization. At least one of a starter, a surfactant, a sensitizer, a UV absorber, a decane coupling agent, a filler, and a dispersant usually contains a solvent, an alkali-soluble resin, and a polymerization initiator. Further, any component selected from the group consisting of a surfactant, a sensitizer, a UV absorber, a decane coupling agent, and a filler may be contained.

Further, a crosslinking agent, a hardening accelerator, an elastomer, an organic carboxylic acid or an organic carboxylic anhydride, a thermosetting accelerator, a thermal polymerization inhibitor, a plasticizer, a coloring agent (coloring pigment or dye), or a substrate surface may be used in combination. Adhesion promoter and other auxiliary agents (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc.).

Hereinafter, the components will be described in detail.

<solvent>

The composition of the present invention can usually be constituted by using a solvent. The solvent is basically not particularly limited as long as it satisfies the solubility of each component or the coating property of the composition. Further, when the composition of the present invention is prepared, two or more solvents may be used.

As the solvent, examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, and isopropyl butyrate. Ester, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl glycolate (eg methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate (eg methyl methoxyacetate) , ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-hydroxypropionate (for example: 3-hydroxypropionate) Ester, ethyl 3-hydroxypropionate, etc. (eg methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ester, etc.)), 2- Alkyl hydroxypropionates (for example: methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, etc. (for example, methyl 2-methoxypropionate, 2-methoxy) Ethyl propyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-oxy-2-methylpropanoic acid Esters and ethyl 2-oxy-2-methylpropanoate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), acetone Methyl ester, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., in addition, as ethers For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl 2 can be suitably used. Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. Examples of the ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone. Aromatic hydrocarbons such as may be suitably include toluene and xylene.

From the viewpoints of solubility of the ultraviolet absorber and the alkali-soluble resin, improvement of the coating surface, and the like, it is also preferred to mix two or more kinds of these solvents. In this case, it is particularly preferred to comprise a methyl ester selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethylene glycol. Methyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol Two or more mixed solutions of methyl ether acetate.

When the composition of the present invention contains a solvent, from the viewpoint of coatability, it is preferred to set the content of the solvent in the composition to the total solid content concentration of the composition. The amount of the solvent in the composition is preferably such that the total solid content of the composition becomes 5% by mass to 60% by mass, and particularly preferably the solvent is used in the composition. The content in the medium is such that the total solid content concentration of the composition becomes 10% by mass to 50% by mass.

<alkali soluble resin>

The composition of the present invention preferably further contains an alkali-soluble resin. By containing an alkali-soluble resin, developability and pattern formation property are improved.

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

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

The monomer having an acid group after the polymerization is, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or a monomer having an epoxy group such as glycidyl (meth)acrylate. A monomer having an isocyanate group such as 2-isocyanatoethyl (meth)acrylate. The single body for introducing an acid group may be only one type, or There are two or more types. When an acid group is introduced into an alkali-soluble resin, for example, a monomer having an acid group and/or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as "a single amount for introducing an acid group" may be used. The body ") can be polymerized as a single component. In addition, when an acid group can be introduced as a monomer component after polymerization, a treatment for imparting an acid group as described later is required after the polymerization.

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

The linear organic high molecular polymer used as the alkali-soluble resin is preferably a polymer having a carboxylic acid in a side chain, and examples thereof include a methacrylic acid copolymer, an acrylic copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. An alkali-soluble phenol resin such as a copolymer of a maleic acid, a partially esterified maleic acid copolymer or a novolak-type resin, or an acidic cellulose derivative having a carboxylic acid in a side chain, and having a hydroxyl group The polymer is added to the anhydride. Copolymers of (meth)acrylic acid with other monoliths copolymerizable therewith are particularly suitable as alkali-soluble resins. Examples of the other monomer to be copolymerizable with (meth)acrylic acid include an alkyl (meth)acrylate, an aryl (meth)acrylate, and a vinyl compound. Examples of the (meth)acrylic acid alkyl ester and the (meth)acrylic acid aryl ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate Ester, toluene (meth)acrylate, naphthalene (meth)acrylate Examples of the vinyl compound, cyclohexyl (meth) acrylate, etc., and examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, and N-ethylene. Pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, etc., as described in Japanese Patent Laid-Open No. Hei 10-300922 Examples of the butylenediimide monomer include N-phenyl maleimide and N-cyclohexylmethyleneimine. Further, these other monomeric substances which can be copolymerized with (meth)acrylic acid may be used alone or in combination of two or more.

The alkali-soluble resin is preferably an alkali-soluble resin which is a compound represented by the following formula (ED) (hereinafter sometimes referred to as "ether dimer"). A polymer obtained by polymerizing a single component as an essential component:

(In the formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent). Thereby, the composition of the present invention can form a cured coating film which is extremely excellent in heat resistance and extremely excellent in transparency. In the above-mentioned general formula of the above-mentioned ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ or R ² is not particularly limited, and examples thereof include a methyl group and an ethyl group. a linear or branched alkyl group such as n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-pentyl, stearyl, lauryl or 2-ethylhexyl; An aryl group such as a phenyl group; an alicyclic group such as a cyclohexyl group, a tert-butylcyclohexyl group, a dicyclopentadienyl group, a tricyclodecanyl group, an isobornyl group, an adamantyl group or a 2-methyl-2-adamantyl group; An alkyl group substituted with an alkoxy group such as 1-methoxyethyl or 1-ethoxyethyl; an alkyl group substituted with an aryl group such as a benzyl group; and the like. Among these bases, from the viewpoint of heat resistance, a substituent of a primary carbon or a secondary carbon which is hard to be removed by acid or heat such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group is particularly preferable.

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

The alkali-soluble phenol resin can be suitably used in the case where the composition of the present invention is made into a positive composition. Examples of the alkali-soluble phenol resin include a novolak resin and a vinyl polymer.

The novolac resin is obtained by, for example, condensing a phenol with an aldehyde in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, or double Phenol A and the like.

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

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

Specific examples of the novolak resin include m-cresol, p-cresol or a condensation product of a mixture of these and formaldehyde.

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

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

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

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

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

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

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

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

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

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

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

Polybenzoxazole can be obtained by reacting a bisaminophenol with a dicarboxylic acid, a corresponding dimethylhydrazine chloride, an active dicarboxylic acid ester or the like. In general, it can be obtained by subjecting polyhydroxyguanamine to dehydration ring closure by chemical treatment by heating or phosphoric anhydride, a base, a carbodiimide compound or the like, and having a dicarboxylic acid residue and a bisaminophenol residue, The polyhydroxy decylamine is one of the polybenzoxazole precursors obtained by reacting a bisaminophenol compound with a dicarboxylic acid. Examples of the acid constituting the dicarboxylic acid residue include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, and bis(carboxyphenyl)hexafluoropropane. Biphenyldicarboxylic acid, diphenylketone dicarboxylic acid, triphenyldicarboxylic acid, and the like. Two or more kinds of the above acids can be used.

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

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

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

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

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

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

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

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

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

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

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

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

Further, it is preferred to block the ends of the resins by a monoamine having an hydroxyl group, a carboxyl group, a sulfonic acid group or a thiol group, an acid anhydride, a hydrazine chloride or a monocarboxylic acid. Two or more of them can be used. By having the above-mentioned base at the end of the main chain, the tree can be easily The rate of dissolution of the lipid to the aqueous alkaline solution is adjusted to a preferred range.

Preferred examples of the monoamine include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, and 1-hydroxy-5-amino group. Naphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-amino group Naphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-amino group Naphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-amine Benzobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-amino group Phenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, and the like. Two or more kinds of the above monoamines can be used.

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

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

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

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

When the alkali-soluble resin is contained, the content in the composition is preferably 30% by mass to 80% by mass, and more preferably 50% by mass to 70% by mass based on the total solid content of the composition. The amount of the alkali-soluble resin may be one or two or more. When two or more kinds are contained, the total amount is in the above range.

<Polymerization initiator>

From the viewpoint of further enhancing the sensitivity, the composition of the present invention preferably further contains a polymerization initiator.

As the polymerization initiator in the present invention, those which are described below as a polymerization initiator can be used.

The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known polymerization initiators. For example, it is preferred that the ultraviolet region has a sensitivity to visible light. Further, it may be an active agent which generates a living radical with a photo-excited sensitizer, and may also be an initiator which starts cationic polymerization corresponding to the type of the monomer.

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

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

Examples of the halogenated hydrocarbon compound having a triazine skeleton include a compound described in J. Lin et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), British Patent No. 1,388,492. The compound described in the specification, the compound described in JP-A-53-133428, the compound described in the specification of German Patent No. 3337024, and the Journal of Organic Chemistry (J. Org. Chem.) by FC Schaefer et al. , the compound described in 1527 (1964), A compound described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The compound or the like described.

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

Further, examples of the polymerization initiator other than the above include an acridine derivative (for example, 9-phenyl acridine, 1,7-bis(9,9'-acridinyl)heptane, etc.), N-benzene. Glycine and the like, polyhalogen compounds (for example, carbon tetrabromide, phenyltribromomethylhydrazine, phenyltrichloromethyl ketone, etc.), coumarins (for example, 3-(2-benzophenone) Benzofuranoyl-7-diethylamine coumarin, 3-(2-benzofurancarbenyl)-7-(1-pyrrolidinyl)coumarin, 3-benzylidene -7-diethylamine coumarin, 3-(2-methoxybenzimidyl)-7-diethylamine coumarin, 3-(4-dimethylaminobenzylidene)- 7-Diethylamine coumarin, 3,3'-carbonylbis(5,7-di-n-propoxycoumarin), 3,3'-carbonyl bis(7-diethyl) Amino coumarin), 3-benzylidene-7-methoxycoumarin, 3-(2-furanyl)-7-diethylamine coumarin, 3-(4-di Ethyl cinnabarinyl)-7-diethylamine coumarin, 7-methoxy-3-(3-pyridylcarbonyl)coumarin, 3-benzylidene-5,7-dipropyl Oxycoumarin, 7-benzotriazol-2-ylcoumarin, and Japanese Patent Laid-Open No. Hei 5-19475, Japanese Patent Laid-Open No. Hei 7-271028, and Japanese Patent Laid-Open No. 2002-363206 In the case of the coumarin compound or the like described in JP-A-2002-363208, JP-A-2002-363208, JP-A-2002-363209, and the like, Bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentyl Phenylphosphine oxide, LucirinTPO, etc.), metallocenes (eg bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-) Base)-phenyl)titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1+)-hexafluorophosphate (1-), etc., Japanese Patent Laid-Open No. Sho 53-133428, Japanese Patent Special Proclamation No. 57-1819, Japan Publication No. Sho 57-6096 Split well, and compounds of U.S. Patent No. 3,615,455 described in the specification.

Examples of the ketone compound include diphenyl ketone, 2-methyl diphenyl ketone, 3-methyl diphenyl ketone, 4-methyl diphenyl ketone, and 4-methoxy diphenyl ketone. , 2-chlorodiphenyl ketone, 4-chlorodiphenyl ketone, 4-bromodiphenyl ketone, 2-carboxydiphenyl ketone, 2-ethoxycarbonyldiphenyl ketone, diphenyl ketone tetracarboxylate Acid or its tetramethyl ester, 4,4'-bis(dialkylamino)diphenyl ketone (eg 4,4'-bis(dimethylamino)diphenyl ketone, 4,4'-double (dicyclohexylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-bis(dihydroxyethylamino)diphenyl ketone, 4-methyl Oxy-4'-dimethylaminodiphenyl ketone, 4,4'-dimethoxy Diphenyl ketone, 4-dimethylaminodiphenyl ketone, 4-dimethylaminoacetophenone, Benzil, hydrazine, 2-tert-butyl fluorene, 2-methyl hydrazine Anthracene, phenanthrenequinone, xanthone, thioxanthone, 2-chloro-thiaxanone, 2,4-diethylthiaxanone, anthrone, 2-benzyl-dimethylamino-1 -(4-morpholinylphenyl)-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone, 2-hydroxy-2 -Methyl-[4-(1-methylvinyl)phenyl]propanol oligomers, benzoin, benzoin ethers (eg benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether) , benzyldimethylketal), acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, and the like.

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

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

As the polymerization initiator, a quinone compound is also preferably exemplified. Specific examples of the oxime-based initiators include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, and the compounds described in JP-A-2006-342166. .

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

As the oxime ester compound, for example, "The British Chemical Society, JC Perkin II" (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, "Light" Compounds described in Journal of Photopolymer Science and Technology, 1995, pp. 202-232, and JP-A-2000-66385, Japanese Patent Laid-Open Publication No. 2000-80068, Japan A compound or the like described in each of the publications of Japanese Laid-Open Patent Publication No. Hei. No. 2006-342166.

Commercially available products such as IRGACURE-OXE 01 (manufactured by BASF Corporation) and IRGACURE-OXE 02 (manufactured by BASF Corporation) can be suitably used.

Further, as the oxime ester compound other than the above, carbazole can also be used. In the N-position, the compound described in Japanese Patent Publication No. 2009-519904, and the compound and the dye moiety described in U.S. Patent No. 7,626,957, to which a heterocyclic group is introduced at the diphenyl ketone site, are attached. A ketone-based compound described in Japanese Laid-Open Patent Publication No. 2010-15025, and a ketone-based compound described in International Patent Publication No. 2009-131189, and a triazine in the same molecule. The compound described in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

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

In addition, the compound described in JP-A-2009-242469, which has an unsaturated bond at a specific site of a ruthenium compound, can be highly reproducible by regenerating a living radical from a polymerization inert radical. Use as appropriate.

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

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

In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

In the above formula (OX-1), a monovalent substituent represented by R is preferably a monovalent non-metal atomic group.

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

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

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

The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and specific examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 9-fluorenyl group. , 9-phenanthryl, 1-fluorenyl, 5-fused tetraphenyl, 1-indenyl, 2-azulene, 9-fluorenyl, triphenyl, biphenyl, o-tolyl, M-tolyl, p-tolyl, xylyl, o- cumyl, m-isopropylphenyl and p-cumyl, 2,4,6-trimethyl, mesityl, cyclopentadienyl, Binaphtyl, bis-naphthyl, tetratetraphthyl, cycloheptatrienyl, bisphenylene, dicyclopentadienyl phenyl, propyl [di] ene fluorenyl, fluorenyl, vinyl hydrazine Base, propylene naphthyl, anthracenyl, fluorenyl, hydrazino, hydrazinyl, hydrazino, fluorenyl, phenanthryl, triphenylene, anthracenyl, fluorenyl, fused tetraphenyl, quinone Alkenyl, fluorenyl, fluorenyl, pentaphenyl, fused pentaphenyl, tetraphenyl, hexaphenyl, hexaphenyl, ruthenyl, fluorenyl, tert-trinaphthyl, heptaphenyl, hexaphenyl Base, base, and base.

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

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

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

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

Specifically, a thienyl group, a benzo[b]thienyl group, a naphtho[2,3-b]thienyl group (naphtho[2,3-b] can be exemplified. Thienyl group), thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, Xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group (pyridyl group), pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-fluorenyl group (3H-indolyl group), indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolizinyl group, isoquinolyl group (isoquinolyl group), quinolyl group, phthalazinyl group, Naphthyridinyl group, quinoxanilyl group, quinazolinyl group, Cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenidinyl group (phenanthridinyl group), acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenarsazinyl group, isothiazolyl ( Isothiazolyl group), phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, different Isochromanyl group, Chromyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazoline Pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, Quinuclidinyl group, morpholinyl group, and thioxantholyl group.

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

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

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

Among them, the structure shown below is particularly preferable.

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

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

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

In the above formula (OX-1), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent. The substituent is the same as the substituent in the substituted aryl group exemplified as a specific example of the aryl group which may have a substituent.

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

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

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

In the formula (OX-2), R and X each independently represent a monovalent substituent, and A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n is an integer of 0-5.

The meanings of R, A, and Ar in the formula (OX-2) and the above formula (OX-1) R, A, and Ar are the same, and preferred examples are also the same.

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

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

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

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

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

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

In the formula (OX-3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0-5.

The meanings of R, X, A, Ar, and n in the formula (OX-3) are the same as those of R, X, A, Ar, and n in the above formula (OX-2), and preferred examples are also the same.

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

The ruthenium compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably a ruthenium compound having a high absorbance at 365 nm and 405 nm.

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

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

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

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

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

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

<Surfactant>

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

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

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

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

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

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, Glycerol ethoxylate, etc., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene decyl phenyl ether, polyethylene glycol lauric Acid ester, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic304, 701, 704, 901, 904, manufactured by BASF Corporation) 150R1), Solsperse20000 (made by Lubrizol (share)), etc.

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

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

Examples of the anthrone-based surfactant include Toray. "Toray Silicone DC3PA", "Toray Silicone SH7PA", "Toray Silicone DC11PA", "Toray Silicone SH21PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Toray Silicone SH30PA", "Toray" manufactured by Dow Corning (share) Silicone SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF-4452" manufactured by Momentive Performance Materials, Shin-Etsu Chemical Industry ( "KP341", "KF6001", "KF6002" manufactured by the company, "BYK307", "BYK323", "BYK330" manufactured by BYK Chemie.

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

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

<sensitizer>

The composition of the present invention may contain a sensitizer for the purpose of increasing the radical generating efficiency of the polymerization initiator and the long wavelength of the photosensitive wavelength. As the sensitizer which can be used in the present invention, it is preferred to sensitize the above photopolymerization initiator with an electron transfer mechanism or an energy transfer mechanism. Examples of the sensitizer which can be used in the present invention include compounds which are exemplified below and which have an absorption wavelength in a wavelength region of from 300 nm to 450 nm.

Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in a region of from 330 nm to 450 nm.

For example, polynuclear aromatics (for example, phenanthrene, anthracene, anthracene, pyrene, and hydrazine) Triphenyl, 9,10-dialkoxypurine, dibenzopyrans (such as fluorescein, blush, erythrosine, Rhodamine B, Bengal rose red) (Rose Bengal)), thioxanthone (2,4-diethylthioxanthone, isopropyl thioxanthone, diethyl thioxanthone, chlorothiazinone), cyanine (eg, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbocyanine), phthalocyanines, thiazides (eg, thionine, methylene blue, A) Aniline blue), acridines (such as acridine orange, chlorsulfurin, acriflavine), terpenoids (such as hydrazine), squaraine guanidine salts (such as squaric acid ylide), acridine orange , coumarins (eg 7-diethylamino-4-methylcoumarin), coumarinones, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenyl Methane, triphenylmethane, distyrylbenzene, carbazole, porphyrin, spiro compound, quinacridone, indigo, styryl, pyranthene, pyrrolemethylene, pyrazolo Oxazole compound, benzothiazole compound, barbituric acid derivative , Thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, m which Le ketone aromatic ketone compound, N- oxazolidinone aryl group and heterocyclic compounds.

These commercially available products can be appropriately selected and used, and examples thereof include Kayacure DETX-S (a thioxanthone compound manufactured by Nippon Kayaku Co., Ltd.).

Further, the compounds described in the specification of the European Patent No. 568,993, the specification of the U.S. Patent No. 4,508,811, the specification of the U.S. Patent No. 5,227,227, the Japanese Patent Laid-Open No. 2001-125255, and the Japanese Patent Laid-Open No. Hei 11-271969 Wait.

The composition may contain a sensitizer or may not contain a sensitizer, and when it contains a sensitizer In the case of the total solid content of the composition of the present invention, the content of the sensitizer is preferably 0,01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 2% by mass or less.

<UV absorber>

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

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

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

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

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

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

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

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

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

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

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

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

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

Among the above, in the present invention, R ^{3 is} preferably a group selected from the group consisting of a cyano group, -COOR ⁵ , -CONHR ⁵ , -COR ⁵ , and -SO ₂ R ⁵ , and further preferably R ⁴ . It is a group selected from the group consisting of a cyano group, -COOR ⁶ , -CONHR ⁶ , -COR ⁶ , and -SO ₂ R ⁶ . R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The meaning of the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by R ⁵ and R ⁶ is the same as in the case of the above R ¹ and R ² , and the preferred embodiment is also the same. .

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

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

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

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

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

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

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

The commercially available product is, for example, a diethylamino-phenylsulfonyl-pentadienoic acid-based ultraviolet absorber (manufactured by FUJIFILM Fine Chemicals, trade name: DPO).

In the present invention, the above various ultraviolet absorbers may be used alone or in combination of two or more.

The composition of the present invention may contain an ultraviolet absorber or may not contain an ultraviolet absorber. When the ultraviolet absorber is contained, the content of the ultraviolet absorber is preferably 0.001% by mass or more based on the total solid content of the composition of the present invention. 1% by mass or less, more preferably 0.01% by mass or more and 0.1% by mass or less.

<decane coupling agent>

In the composition of the present invention, a decane coupling agent can be used from the viewpoint of further improving the adhesion to the substrate.

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

That is, as the decane coupling agent used in the present invention, a compound having an alkoxyalkyl group, a (meth) acryl fluorenyl group or an epoxy group is preferable, and specifically, it can be listed. The (meth)acryloyl-trimethoxydecane compound, glycidyl-trimethoxydecane compound, etc. which have the following structures are mentioned.

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

The amount of the total solid content in the composition used in the present invention is preferably in the range of 0.1% by mass to 5.0% by mass, as the amount of the decane coupling agent used. More preferably, it is 0.2 mass% - 3.0 mass%.

<filler>

The composition of the present invention may further contain a filler. Examples of the filler which can be used in the present invention include spherical cerium oxide which has been surface-treated with a decane coupling agent.

When the composition of the present invention contains a filler, it is preferable from the viewpoint of obtaining a pattern having high durability (in particular, when the wiring density of the metal wiring covered with the solder resist is high, the solder resist is required to be more durable. In the case of sex, the above effects are remarkable).

By using a spherical cerium oxide surface-treated with a decane coupling agent, the composition has improved thermal cycle test resistance and storage stability, for example, after undergoing a harsh environment such as a heat cycle test. The same good shape as that immediately after the pattern formation can be maintained.

In addition, the "spherical shape" in the spherical filler means that the shape of the particles is not needle-shaped, columnar, or amorphous, and it is not necessary to be "true spherical" as long as it has a curvature, but it is representative. The "spherical shape" can be referred to as "true spherical shape".

The filler is spherical and can be confirmed by observation using a scanning electron microscope (SEM).

The volume average particle diameter of the primary particles of the filler is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.05 μm to 3 μm, more preferably 0.1 μm to 1 μm. It is advantageous when the volume average particle diameter of the primary particles of the above filler is within the above range, because the decrease in workability due to the appearance of thixotropy is suppressed. Since the maximum particle diameter does not become large, the adhesion of the foreign matter in the obtained cured film or the generation of defects caused by the unevenness of the coating film is suppressed.

The volume average particle diameter of the primary particles of the above filler can be measured by a dynamic light scattering particle size distribution measuring apparatus.

The above filler may be dispersed by using a dispersing agent or a binder. As described above, from the viewpoint of hardenability, an alkali-soluble binder polymer having a crosslinkable group in a side chain is particularly preferred.

- Surface treatment -

Next, the surface treatment of the filler will be described. The surface treatment of the filler is not particularly limited and may be appropriately selected according to the purpose, but it is preferably a treatment of coating cerium oxide by a decane coupling agent.

-decane coupling agent -

The decane coupling agent used for the surface treatment of the filler is not particularly limited and may be appropriately selected according to the purpose, but is preferably at least selected from the group consisting of an alkoxyalkyl group, a chloroalkyl group, and an ethoxyalkyl group. One type of functional group (hereinafter also referred to as "first functional group"), and at least one functional group selected from the group consisting of a (meth) acrylonitrile group, an amine group, and an epoxy group (hereinafter, also referred to as "second The functional group "), the second functional group is more preferably a (meth) acrylonitrile group or an amine group, and the second functional group is more preferably a (meth) acrylonitrile group. If the second functional group is (methyl group) The acrylonitrile group is advantageous from the viewpoint of storage stability or thermal cycle test (TCT) tolerance.

Further, a decane coupling agent described in Japanese Patent Publication No. Hei 7-68256, which has an alkoxydecane selected from the group, is also preferably used. At least one of a group, a chloroalkylene group, and an ethoxylated decyl group is a first functional group, and at least one selected from the group consisting of an imidazole group, an alkylimidazolyl group, and a vinylimidazolyl group is used as the second functional group. base.

The decane coupling agent is not particularly limited, and examples thereof include γ-aminopropyltriethoxydecane and N-(β-aminoethyl)-γ-aminopropyltrimethoxydecane. , N-(β-Aminoethyl)-γ-aminopropylmethyldimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldi Methoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, γ-methyl propylene methoxy propyl methyl dimethoxy decane, as described in Japanese Patent Publication No. Hei 7-68256 α-[[3-(Trimethoxydecyl)propoxy]methyl]-imidazol-1-ethanol, 2-ethyl-4-methyl-α-[[3-(trimethoxydecyl) Propyloxy]methyl]-imidazol-1-ethanol, 4-vinyl-α-[[3-(trimethoxydecyl)propyloxy]methyl]-imidazole-1-ethanol, 2-B 4-methylimidazolyltrimethoxydecane, and salts, intramolecular condensates, intermolecular condensates, and the like. These decane coupling agents may be used alone or in combination of two or more.

The surface treatment of the spherical cerium oxide by the decane coupling agent may be performed only in advance of the spherical cerium oxide (hereinafter referred to as "pretreatment"), or in the composition Some or all of the other fillers contained are treated together.

The method for pretreatment is not particularly limited, and examples thereof include a dry method, an aqueous solution method, an organic solvent method, and a spray method. The temperature at which the pretreatment is carried out is not particularly limited, but is preferably from room temperature to 200 °C.

It is also preferable to add a catalyst when performing pretreatment. The catalyst is not particularly limited, and examples thereof include an acid, a base, a metal compound, and an organometallic compound.

The amount of the decane coupling agent to be added in the pretreatment is not particularly limited, and is preferably in the range of 0.01 part by mass to 50 parts by mass, more preferably 0.05 part by mass to 50% by mass based on 100 parts by mass of the spherical cerium oxide. The scope of the share. When the amount of addition is within the above range, a surface treatment sufficient for the effect of development can be performed, and the decrease in handleability due to aggregation of the spherical cerium oxide after the treatment can be suppressed.

The decane coupling agent reacts with the surface of the substrate, the spherical ceria surface, and the active group of the binder by the first functional group, and further reacts the second functional group with the carboxyl group and the ethylenically unsaturated group of the binder. Therefore, it has the function of improving the adhesion between the substrate and the photosensitive layer. On the other hand, since the above-mentioned decane coupling agent has high reactivity, when it is added to the composition, there is a case where the second functional group is mainly reacted or deactivated during storage in the storage process due to diffusion. The shelf life or pot life becomes shorter.

However, if the spherical ceria is pretreated with a decane coupling agent as described above, the diffusion action is suppressed, and the problem of shelf life or pot life is greatly improved, and it can also be produced. One liquid type. Further, when the spherical cerium oxide is pretreated, the conditions such as the stirring condition, the temperature condition, and the use of the catalyst can be freely selected, so that it can be remarkably improved as compared with the case where the pretreatment is not added. The reaction rate between the first functional group of the decane coupling agent and the active group in the spherical cerium oxide. Therefore, very good results can be obtained particularly in the demanding characteristics such as electroless gold plating, electroless plating soldering, and moisture load resistance test. In addition, borrow By performing the above pretreatment, the amount of the decane coupling agent used can be reduced, and the shelf life and pot life can be further improved.

As the spherical cerium oxide which has been surface-treated by the decane coupling agent which can be used in the present invention, for example, the electrochemistry industry: FB, SFP series, Ronson: 1-FX, East Asian synthesis: HSP series, Fuso Chemical Industry: SP series, etc.

The composition may or may not contain a filler. When the filler is contained, the content of the filler relative to the total solid content of the composition is not particularly limited, and may be appropriately selected according to the purpose, but is preferably 1 of the total solid content. The mass % to 40% by mass, more preferably 2% by mass to 30% by mass, still more preferably 3% by mass to 20% by mass. When the amount of addition is within the above range, a sufficient decrease in the coefficient of linear expansion is achieved, and embrittlement of the formed cured film is suppressed, and the function as a protective film for wiring when wiring is formed using a permanent pattern is sufficiently exhibited.

<dispersant>

In the present invention, in particular, when the tungsten compound is tungsten fine particles, in order to enhance the dispersibility and dispersion stability of the tungsten compound in the composition, it can be used after being dispersed by a known dispersing agent.

As the dispersant which can be used in the present invention, a polymer dispersant (for example, polyamine amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polycondensation) are exemplified. Ester, modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalenesulfonic acid formaldehyde condensate], and polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkanolamine and other interfaces Active agent, etc.

The polymer dispersant can be further classified into a linear high according to its structure. Molecules, terminal modified polymers, graft polymers, and block polymers.

The terminal-modified polymer having a fixed portion on the surface is, for example, a high-phosphoric acid group at the terminal described in JP-A-3-112992, JP-A-2003-533455, and the like. A polymer having a sulfonic acid group at the terminal, as described in JP-A-2002-273191, and a partial skeleton or a heterocyclic ring having an organic dye described in Japanese Laid-Open Patent Publication No. Hei 9-77994. A polymer produced by modifying an oligomer or a polymer having a hydroxyl group or an amine group at one end and an acid anhydride, as described in JP-A-2008-29901, and the like. In addition, two or more fixed sites (acid groups, basic groups, partial skeletons of organic dyes, heterocyclic rings, etc.) for the surface of the infrared shielding material are introduced into the polymer end as described in JP-A-2007-277514. The dispersion stability of the polymer is also excellent, and is preferable.

For example, JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, and the like are exemplified. The reaction product of the poly(allyl alkylene imine) and the polyester described in the above, and the reaction product of the polyallylamine and the polyester described in Japanese Patent Laid-Open Publication No. Hei 9-169821, etc., Japanese Patent Laid-Open No. 2009- The amphoteric dispersion resin having a basic group and an acidic group, and the macromonomer and nitrogen atom described in JP-A-2004-37986, and the like. The monomer copolymer is organic as described in JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, and the like. A copolymer of a macromolecular monomer and an acid group-containing monomer described in JP-A-2010-106268, and the like.

As a macromonomer to be used for the production of a graft-type polymer having a fixed portion on the surface by radical polymerization, a known macromonomer can be used, and examples thereof include macromolecules manufactured by East Asia Synthetic Co., Ltd. Monomer AA-6 (polymethyl methacrylate with terminal group of methacryl fluorenyl), AS-6 (polystyrene with terminal methacryloyl group), AN-6S (terminal group is methyl Acrylate-based copolymer of styrene and acrylonitrile), AB-6 (polybutyl acrylate of methacryl fluorenyl group), Placcel FM5 (Methyl) manufactured by Daicel Chemical Industry Co., Ltd. Ε-caprolactone 5 molar equivalent adduct of 2-hydroxyethyl acrylate), FA10L (ε-caprolactone 10 molar equivalent adduct of 2-hydroxyethyl acrylate), and Japanese Patent Special Open 2 A polyester-based macromonomer described in the publication No. -272009. Among these, in particular, from the viewpoint of dispersibility of the infrared shielding material in the composition, dispersion stability, and developability exhibited by the composition using the infrared shielding material, it is particularly preferable that it is soft and solvophilic. A polyester-based macromonomer represented by the polyester-based macromonomer described in JP-A No. 2-272009 is preferred.

The block type polymer described in the above-mentioned Japanese Patent Publication No. 2003-49110, and the like.

Further, a known dispersant or surfactant can be appropriately selected and used.

As such a specific example, "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylate), 110 (acid group-containing copolymer), 130 (polyamide) manufactured by BYK Chemical Co., Ltd. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", "EFKA4047, 4050~4010" manufactured by EFKA ~4165 (polyurethane type), EFKA4330~4340 (block copolymer), 4400~4402 (modified polyacrylate), 5010 (polyester decylamine), 5765 (high molecular weight polycarboxylate) 6220 (fatty acid polyester), 6745 (anthraquinone derivative), "Ajisper PB821, PB822, PB880, PB881" manufactured by Ajinomoto Fine-Techno Co., Ltd., "Florene TG-710 (amine) manufactured by Kyoeisha Chemical Co., Ltd. "Carbide oligomer"), "Polyflow No. 50E, No. 300 (acrylic copolymer)", "Disparlon KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid) manufactured by Nanben Chemical Co., Ltd. ), #7004 (polyether ester), DA-703-50, DA-705, DA-725", "Demol RN, N (naphthalenesulfonic acid formaldehyde polycondensate), MS, C, SN- manufactured by Kao Corporation B (aromatic sulfonate Formaldehyde polycondensate), "Homogenol L-18 (polymer polycarboxylic acid)", "Emalgen 920, 930, 935, 985 (polyoxyethylene decyl phenyl ether)", "Acetamin86 (stearylamine acetate) "Solsperse 5000 (anthraquinone derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer with a functional part at the end), 24000, 28000, 32000, manufactured by Lubrizol, Japan. 38500 (grafted polymer)", Nikol T106 (polyoxyethylene sorbitan monooleate) and MYS-IEX (polyoxyethylene monostearate) manufactured by Nikko Chemicals Co., Ltd. Hinoact T-8000E manufactured by Kawaken Fine Chemicals Co., Ltd. Etc., KP341, an organic siloxane polymer manufactured by Shin-Etsu Chemical Co., Ltd., "W001: Cationic surfactant" manufactured by Yushang Co., Ltd., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, poly Nonionics such as oxyethylene ether, polyoxyethylene octyl phenyl ether, polyoxyethylene decyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester An interfacial surfactant, an anionic surfactant such as "W004, W005, W017", "EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer100, EFKA Polymer400, EFKA Polymer401, EFKA Polymer450 manufactured by Morishita Industrial Co., Ltd." "Disperse Aid6, Disperse Aid8, Disperse Aid15, Disperse Aid9100" and other polymer dispersants manufactured by Sannopco (shares), "Adeka Pluronic L31, F38" manufactured by ADEKA (shares) , "L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123", and "Ionet (trade name) manufactured by Sanyo Chemical (share)" S-20" and so on.

These dispersing agents may be used singly or in combination of two or more. Further, the dispersing agent of the present invention may be used by using the terminal modified polymer having a fixed portion on the surface of the infrared shielding material, a graft polymer, a block polymer, and an alkali-soluble resin. Examples of the alkali-soluble resin include a (meth)acrylic copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and the like, and a side chain. An acidic cellulose derivative having a carboxylic acid, a resin to which an acid anhydride is added to a polymer having a hydroxyl group, and particularly preferably a (meth)acrylic copolymer. In addition, it is noted in Japanese Patent Laid-Open No. Hei 10-300922. The N-position-substituted maleimide-imine monomer copolymer, the ether-dimer copolymer described in JP-A-2004-300204, and the Japanese Patent Application Laid-Open No. Hei 7-319161 An alkali-soluble resin containing a polymerizable group is also preferred.

From the viewpoint of dispersibility, developability, and precipitability, the resin described below is preferably the one described in JP-A-2010-106268, and particularly preferably from the viewpoint of dispersibility. The polymer dispersing agent having a polyester chain in the chain is preferably a resin having an acid group and a polyester chain from the viewpoint of dispersibility and resolution of a pattern formed by photolithography. The acid group in the dispersant is preferably an acid group having a pKa of 6 or less from the viewpoint of adsorptivity, and particularly preferably a carboxylic acid, a sulfonic acid or a phosphoric acid.

Hereinafter, the dispersion resin described in JP-A-2010-106268, which is preferably used in the present invention, will be described.

A preferred dispersant is a graft copolymer of a graft chain selected from the group consisting of a polyester structure, a polyether structure, and a polyacrylate structure in a molecule having a number of atoms other than a hydrogen atom in the range of 40 to 10,000. It is preferable that at least the structural unit represented by any one of the following formulas (1) to (4) is contained, and it is more preferable to contain at least the following formula (1A), the following formula (2A), and the following A structural unit represented by any one of the formula (3A), the following formula (3B), and the following (4).

In the formulae (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH, and particularly preferably an oxygen atom.

In the formulae (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ and X ⁵ are preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a group, from the viewpoint of limitations in terms of synthesis. Base, especially good for methyl.

In the formulae (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a divalent linking group, and the structure is not particularly limited. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ and Y ⁴ include the following (Y-1) to (Y-21) linking groups. In the following structures, A and B respectively represent a bond to the left terminal group and the right terminal group in the formulae (1) to (4). Among the structures shown below, (Y-2) and (Y-13) are more preferable in terms of ease of synthesis.

In the formulae (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a monovalent organic group, and the structure is not particularly limited, and specific examples thereof include an alkyl group, a hydroxyl group, and an alkoxy group. a aryl group, an aryloxy group, or a heteroaryloxy group, an alkyl sulfide group, an aryl sulfide group, or a heteroaryl sulfide group, an amine group, or the like. Among them, as the monovalent organic group represented by Z ¹ , Z ² , Z ³ and Z ⁴ , in particular, from the viewpoint of improving dispersibility, it is preferred to have a steric repulsion effect as Z ¹ to Z ³ The organic group to be represented is preferably an alkyl group having 5 to 24 carbon atoms or an alkoxy group having 5 to 24 carbon atoms, and particularly preferably a branched alkane having 5 to 24 carbon atoms. An alkoxy group or alkoxy group having a cyclic alkyl group having 5 to 24 carbon atoms. Further, as the organic group represented by Z ⁴ , an alkyl group each independently having a carbon number of 5 to 24 is preferable, and among them, a branched alkyl group having a carbon number of 5 to 24 or a carbon number is preferably used. a cyclic alkyl group of 5 to 24.

In the formulas (1) to (4), n, m, p, and q are each an integer of 1 to 500.

Further, in the formulas (1) and (2), j and k each independently represent an integer of 2 to 8. From the viewpoints of dispersion stability and developability, j and k in the formulae (1) and (2) are preferably an integer of 4 to 6, and most preferably 5.

R ³ in the formula (3) represents a branched or linear alkylene group. R ³ in the formula (3) is preferably an alkylene group having a carbon number of 1 to 10, more preferably an alkylene group having a carbon number of 2 or 3.

R ⁴ in the formula (4) represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. R ⁴ in the formula (4) is preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R ⁴ in the formula (4) is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a carbon number. The cyclic alkyl group having 5 to 20 is more preferably a linear alkyl group having 1 to 20 carbon atoms, and particularly preferably a linear alkyl group having 1 to 6 carbon atoms. Further, as R ⁴ in the formula (4), two or more kinds of R ⁴ having different structures may be used in combination in the graft copolymer.

In the graft copolymer, the structural unit represented by the formula (1) to the formula (4) is preferably contained in a range of 10% to 90% in terms of mass, based on the total mass of the graft copolymer. More preferably, the structural unit represented by the formula (1) to the formula (4) is contained in the range of 30% to 70%. When the structural unit represented by the formula (1) to the formula (4) is contained in the range, the dispersibility of the pigment is high, and the developability when the light-shielding film is formed is good.

Further, the graft copolymer may contain two or more kinds of graft copolymers having different structures.

The structural unit represented by the above formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability and developability.

In addition, the structural unit represented by the above formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability.

In the formula ^{(1A), 1, Y 1} , Z 1 , and the same ^{n X 1, Y 1, Z} 1 and n have the meanings of formula X (1) is, preferred ranges are also the same.

In formula ^{(2A), X 2, Y} 2, Z 2 and m are as defined for the formula X (2) is ^2, Y ^2, Z ² and the same as m, the preferred ranges are also the same.

In addition, the structural unit represented by the above formula (3) is more preferably a structural unit represented by the following formula (3A) or the following formula (3B) from the viewpoint of dispersion stability and developability.

Formula (3A) or the formula (3B) in, X ^3, Y ^3, Z ³ and p are the meanings (3) the formula in which X ^3, Y ^3, Z ³ and the same p, preferred ranges are also the same.

The graft copolymer is more preferably a structural unit represented by the above formula (1A).

Specific examples thereof include the compounds shown below. In addition, among the following exemplified compounds, the numerical value (the numerical value collectively described in the main chain repeating unit) which is described in each structural unit is the content of the structural unit [% by mass: described as (wt%)]. The numerical value described in the repeated portion of the side chain together indicates the number of repetitions of the repeated portion.

As the dispersing agent in the present invention, a compound having a polyester chain as exemplified as the compound 72 is preferred.

The content of the dispersing agent in the preparation of the pigment dispersion in the present invention is preferably from 1% by mass to 90% by mass based on the total solid content of the coloring agent (including the black pigment and other coloring agents) in the pigment dispersion. More preferably, it is 3 mass% to 70 mass%.

When a dispersing agent is used, from the viewpoint of improving dispersibility, it is preferred to first prepare a dispersion composition by a tungsten compound (and optionally other infrared shielding materials as described above), a dispersing agent, and a suitable solvent, and then to prepare a dispersion composition. To the composition of the present invention.

The composition of the present invention may contain a dispersant or may not contain a dispersant. When the dispersant is contained, the content of the dispersant in the dispersion composition is the sum of the total solid content of the infrared shielding particles in the dispersion composition. It is preferably from 1% by mass to 90% by mass, more preferably from 3% by mass to 70% by mass.

The amount of the dispersant composition in the case where the solder resist composition of the present invention contains the dispersant composition is preferably from 1% by mass to 30% by mass, and more preferably from 2% by mass to 10% by mass, based on the total solid content.

<Organic carboxylic acid, organic carboxylic anhydride>

The composition of the present invention may also contain an organic carboxylic acid having a molecular weight of 1,000 or less and/or an organic carboxylic anhydride.

Specific examples of the organic carboxylic acid compound include an aliphatic carboxylic acid or an aromatic carboxylic acid. Examples of the aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, glycolic acid, acrylic acid, and methacrylic acid, oxalic acid, malonic acid, and the like. Succinic acid, glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, etc. a dicarboxylic acid such as dicarboxylic acid, 1,2,3-propanetricarboxylic acid or cephalosporic acid. In addition, examples of the aromatic carboxylic acid include a carboxylic acid in which a carboxyl group such as benzoic acid or phthalic acid is directly bonded to a phenyl group, and a carboxylic acid in which a carboxyl group is bonded to a phenyl group via a carbon bond. Among these, a molecular weight of 600 or less, particularly a molecular weight of 50 to 500 is particularly preferable. Specifically, for example, maleic acid, malonic acid, succinic acid, and itaconic acid are preferable.

Examples of the organic carboxylic acid anhydride include an aliphatic carboxylic acid anhydride and an aromatic carboxylic acid anhydride. Specific examples thereof include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, and succinic anhydride. , maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylate An aliphatic carboxylic acid anhydride such as an acid anhydride. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, a molecular weight of 600 or less, especially a molecular weight of 50 to 500 is particularly preferable, and specifically, for example, maleic anhydride, succinic anhydride, and lemon are preferable. Kang anhydride, itaconic anhydride.

When the organic carboxylic acid and/or the organic carboxylic acid anhydride is contained, the amount of the total solid content is usually 0.01% by mass to 10% by mass, preferably 0.03% by mass to 5% by mass, more preferably 0.05% by mass. %~3 mass% range.

By adding these organic carboxylic acids having a molecular weight of 1,000 or less and/or an organic carboxylic anhydride, it is possible to further reduce the residual of the undissolved matter of the composition while maintaining high pattern adhesion.

The above-mentioned crosslinking agent is described in detail in paragraphs [0166] to [0182] of JP-A-2012-003225, the contents of which are incorporated herein by reference.

The above-mentioned hardening accelerator is described in detail in the paragraph [0241] of JP-A-2012-003225, the content of which is incorporated herein by reference.

The above-mentioned elastomer is described in detail in paragraph [0242] to paragraph [0254] of Japanese Patent Laid-Open Publication No. 2012-003225, the contents of which are incorporated herein by reference.

The above-mentioned thermal polymerization inhibitor is described in detail in paragraphs [0101] to [0102] of JP-A-2008-250074, the contents of which are incorporated herein by reference.

The plasticizer is described in detail in paragraphs [0103] to [0104] of JP-A-2008-250074, the contents of which are incorporated herein by reference.

Regarding the coloring agent described above, for example, paragraph number [0105] to paragraph number [0106] of Japanese Patent Laid-Open Publication No. 2008-250074 or paragraph number [0038] of paragraph No. [0039] of JP-A-2009-205029 It is described in detail and its contents are incorporated into the specification of the present application.

The above-mentioned adhesion promoter is described in detail in paragraphs [0107] to [0109] of JP-A-2008-250074, the contents of which are incorporated herein by reference.

The additives described in these publications can be used in the composition of the present invention.

In order to remove foreign matter, reduce defects, and the like, it is preferred to filter the curable composition of the present embodiment by a filter. It is not particularly limited as long as it is a filter used for filtration purposes or the like from the past. For example, a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon-6 or nylon-6, 6 or a polyolefin resin such as polyethylene or polypropylene (high density) may be used. A filter containing ultra-high molecular weight or the like. Among these materials, polypropylene (including high density polypropylene) is preferred.

The pore diameter of the filter is suitably from about 0.01 μm to about 7.0 μm, preferably from about 0.01 μm to about 2.5 μm, more preferably from about 0.01 μm to about 1.5 μm. By setting it as this range, the fine foreign material which mix|blended into the to-dissolved composition, and the formation of the uniform and smooth composition in the subsequent process can be reliably removed.

Different filters can also be combined when using filters. At this time, the filtration by the first type of filter may be performed only once or twice or more. When two or more filters are combined for different filters, it is preferably second. The pore size after the secondary filtration is larger than the pore diameter of the first filtration. Further, the first type of filters having different pore diameters may be combined in the above range. The aperture here can be referred to the nominal value of the filter manufacturer. As a commercially available filter, for example, from Japan Pall Co., Ltd., Advantec Toyo Co., Ltd., Japan Nihon Entegris Co., Ltd. (formerly Japan Mico) Choose from various filters provided by Mykrolis Co., Ltd. or Kitz Microfilter Co., Ltd.

As the second filter, a filter formed of the same material as that of the above-described first filter can be used. The pore diameter of the second filter is suitably from about 0.5 μm to about 7.0 μm, preferably from about 2.5 μm to about 7.0 μm, more preferably from about 4.5 μm to about 6.0 μm. By setting it as the range, it is possible to remove the foreign matter which is mixed into the mixed liquid in a state in which the component particles contained in the mixed liquid remain, and which hinders the preparation of the uniform and smooth composition in the subsequent step.

For example, the filtration by the first type of filter may be carried out only in the dispersion, and after the other components are mixed, the second filtration is performed.

The use of the composition of the present invention is not particularly limited, and examples thereof include a composition for a solder resist, a composition for a light-shielding film on the back surface of a tantalum substrate in a solid-state image sensor, and a composition for a light-shielding film of a wafer-level lens. A composition for a solder resist is preferred.

When the composition of the present invention is a composition for a solder resist, the solid content concentration is preferably 30% by mass or more and 80% by mass or less, more preferably 35% by mass or more and 70% by mass, in order to form a coating film having a relatively large thickness. Hereinafter, the optimum is 40% by mass or more. 60% by mass or less.

In addition, the viscosity of the composition of the present invention is preferably at 1 mPa. Above s, 3000mPa. Within the range of s below, more preferably 10mPa. Above s, 2000mPa. The range below s, the best is 100mPa. Above s, 1500mPa. s the following range.

When the composition of the present invention is a composition for a solder resist, it is preferably at 10 mPa from the viewpoint of thick film formability and uniform coating properties. Above s, 3000mPa. Within the range of s below, more preferably 500mPa. Above s, 1500mPa. The range below s, the best is 700mPa. Above s, 1400mPa. s the following range.

The present invention also relates to a cured film (preferably a photosensitive layer) formed from the above composition of the present invention. Since the photosensitive layer is formed of the composition of the present invention, it has high light-shielding property in the infrared region, high light transmittance in the visible light region, and has a desired shape and durability (for high temperature and high humidity) A photosensitive layer having an excellent pattern of durability or adhesion to a substrate.

Further, the present invention relates to a permanent pattern formed by the above composition of the present invention. The permanent pattern of the present invention is obtained by exposing and alkali-developing the photosensitive layer formed of the composition of the present invention, and since the composition of the present invention is used, the light-shielding property in the infrared region is high, and in the visible light region It has a high light transmittance, and has a desired shape and durability (a durability against high temperature, high humidity, adhesion to a substrate, etc.).

Further, the present invention includes a step of applying the solder resist composition of the present invention to a substrate; and a step of patternwise exposing the solder resist composition. More specifically, the present invention also relates to a pattern forming method, which in turn includes: using The step of forming a photosensitive layer by the composition of the present invention; the step of patternwise exposing the photosensitive layer to harden the exposed portion; and the step of removing the unexposed portion by alkali development to form a permanent pattern.

Hereinafter, a method of forming a permanent pattern will be described in detail by taking a pattern-shaped solder resist using the composition of the present invention as an example. However, the following description of the type or amount of the solvent for preparing the coating liquid, the coating method of the coating liquid, the thickness of the photosensitive layer, the exposure step, or other steps are not limited to the use of the solder resist. Further, a case where a composition is used to form a photosensitive layer (composition layer) is exemplified here.

-Photosensitive layer -

When a pattern-like solder resist (solder resist pattern) is to be formed, the photosensitive layer is first formed by the above-described composition of the present invention. The photosensitive layer is not particularly limited as long as it is a layer containing the above composition, and the film thickness, the laminated structure, and the like can be appropriately selected depending on the purpose.

As a method of forming the photosensitive layer, a coating liquid obtained by dissolving, emulsifying or dispersing the above-described composition of the present invention in water or a solvent is prepared, and then the coating liquid is directly applied to a substrate. It is dried and dried to form a photosensitive layer.

The solvent for preparing the coating liquid is not particularly limited, and may be any solvent which can uniformly dissolve or disperse the components of the composition of the present invention, and may be appropriately selected according to the purpose, and examples thereof include methanol, ethanol, and Alcohols such as propanol, isopropanol, n-butanol, second butanol, n-hexanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, cyclohexanone , ketones such as cyclopentanone; ethyl acetate, Esters such as butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, propylene glycol monomethyl ether acetate, and methoxypropyl acetate; An aromatic hydrocarbon such as toluene, xylene, benzene or ethylbenzene; a halogenated hydrocarbon such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, dichloromethane or monochlorobenzene; Ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol, propylene glycol monomethyl ether; dimethylformamide, dimethylacetamide , dimethyl hydrazine, cyclobutyl hydrazine, and the like. These solvents may be used alone or in combination of two or more. Further, a known surfactant can also be added.

The method of applying the coating liquid onto the substrate is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include a spin coater, a slit rotary coater, a roll coater, a die coater, and a curtain. A method of coating a curtain coater or the like.

In addition, the drying conditions of the coating film differ depending on the type of each component, the solvent, the use ratio, etc., but it is usually dried at a temperature of 60 ° C to 150 ° C for about 30 seconds to 15 minutes.

The thickness of the photosensitive layer is not particularly limited and may be appropriately selected depending on the intended purpose, and is, for example, preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm, and particularly preferably 4 μm to 30 μm.

(Solder resist pattern forming method)

The method of forming the pattern-cured film using the solder resist composition of the present invention includes at least a step of performing pattern exposure, and further, a development step including selection of suitable conditions, and other steps, as usual. Further, in the present invention, "exposure" is radiation irradiation including not only light of various wavelengths but also electron beams, X-rays, and the like. The meaning to use.

<Exposure step>

The exposure step is a step of exposing the photosensitive layer formed of the above-described composition layer through a mask, and in this step, only the region irradiated with light is hardened.

The exposure is preferably performed by irradiation of radiation, and as the radiation which can be used for exposure, ultraviolet rays or visible light such as an electron beam, KrF, ArF, g-ray, h-ray, or i-ray can be preferably used. Preferred are KrF, g-ray, h-ray, and i-ray.

Examples of the exposure method include stepwise exposure or exposure using a high pressure mercury lamp.

The exposure amount is preferably ⁵ mJ/cm ² to 3000 mJ/cm ² , more preferably 10 mJ/cm ² to 2000 mJ/cm ² , and most preferably 50 mJ/cm ² to 1000 mJ/cm ² .

<other steps>

The other steps are not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include a surface treatment step of a substrate, a development step, a hardening treatment step, and a post-exposure step.

<Development step>

After the exposure step, an alkali development treatment (development step) is performed, and the unexposed portion of the light in the exposure step is eluted into the alkaline aqueous solution. Thereby, a pattern-form solder resist which remains only by photohardening and has a light-shielding property is formed.

As the developer, an organic alkaline developer which does not cause damage to the circuit of the substrate or the like is preferable. As the development temperature, it is usually 20 ° C ~ 40 ° C, and the development time is 10 seconds to 180 seconds.

As the base to be used for the developer, for example, an alkaline aqueous solution is used, that is, a concentration of usually 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass, using pure water to ammonia water or ethylamine. , diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5,4,0]-7 An alkaline aqueous solution obtained by diluting an organic basic compound such as undecene. Further, when a developer containing such an aqueous alkaline solution is used, it is usually washed (rinsed) with pure water after development.

<hardening treatment step>

The hardening treatment step is a step of hardening the photosensitive layer in the formed pattern after performing the above-described development step, and by performing the treatment, the mechanical strength of the permanent pattern is improved.

The hardening treatment step is not particularly limited, and may be appropriately selected depending on the purpose. For example, a total exposure treatment, a total heat treatment, or the like can be suitably mentioned.

As a method of the full exposure treatment, for example, a method of exposing the entire surface of the laminate having the patterned photosensitive layer after the development step may be mentioned. By the overall exposure, the hardening of the polymer component in the composition forming the photosensitive layer is promoted, and the hardening of the permanent pattern is further progressed, and the mechanical strength and durability are improved.

The apparatus for performing the above-described overall exposure is not particularly limited, and may be appropriately selected depending on the purpose. For example, an ultraviolet (UV) exposure machine such as an ultrahigh pressure mercury lamp can be suitably used.

Further, as a method of the overall heat treatment, for example, a method of heating the entire surface of the laminate having the patterned photosensitive layer after the development step may be mentioned. The film strength of the pattern can be increased by full heating.

The heating temperature at the time of full heating is preferably from 120 ° C to 250 ° C. When the heating temperature is 120° C. or higher, the film strength is increased by heat treatment, and when the heating temperature is 250° C. or lower, decomposition of the resin in the above composition is prevented, and the film quality is weakened and becomes brittle. Happening.

The heating time in the case of full heating is preferably from 3 minutes to 180 minutes, more preferably from 5 minutes to 120 minutes.

The apparatus for performing overall heating is not particularly limited, and may be appropriately selected from known apparatuses depending on the purpose, and examples thereof include a drying oven, a hot plate, and an infrared (IR) heater.

The patterned resist formed in the above manner has a wide range of applications because of its excellent infrared shielding properties. Since the composition of the present invention is excellent in the shielding property in the infrared region and the light transmittance in the ultraviolet region to the visible region, a pattern having an excellent shape is formed, and the formed pattern (cured film) has excellent infrared shielding properties. Therefore, it is useful for a device for forming a photodiode having sensitivity to the infrared region, in particular, a solder resist for a solid-state image sensor.

As described above, the composition of the present invention is useful not only for forming a solder resist but also for forming a light shielding film for the back surface of the germanium substrate in the solid-state image sensor or a light shielding film for the wafer level lens.

Thus, the invention also relates to a form having the composition of the invention A solid image sensor having a permanent pattern.

Hereinafter, a solid-state imaging device according to an embodiment of the present invention will be described with reference to FIGS. 1 and 2, but the present invention is not limited to the following specific examples.

In addition, in FIGS. 1 and 2, the same portions are denoted by the same reference numerals.

In addition, in the description, "upper", "upper" and "upper side" refer to the side away from the substrate 10, and "lower", "lower" and "lower side" refer to the side closer to the substrate 10 .

1 is a schematic cross-sectional view showing a configuration of a camera module including a solid-state image sensor of a specific example of the above-described embodiment.

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

Specifically, the camera module 200 includes a solid-state imaging device substrate 100 including an imaging element portion on the first main surface of the substrate, and a first main surface side of the solid-state imaging device substrate 100. The glass substrate 30 (translucent substrate), the infrared cut filter 42 disposed above the glass substrate 30, and the lens disposed above the glass substrate 30 and the infrared cut filter 42 and having an imaging lens 40 in the internal space The shelf 50 and the light-shielding/electromagnetic shield 44 are disposed so as to surround the periphery of the solid-state imaging device substrate 100 and the glass substrate 30. Each member is adhered by the adhesive 20, the adhesive 41, the adhesive 43, and the adhesive 45.

In the camera module 200, the incident light hν from the outside passes through the imaging lens 40, the infrared cut filter 42, and the glass substrate 30 in sequence, and reaches the solid photo. The image sensor element portion of the element substrate 100 is used.

Further, the camera module 200 is connected to the circuit board 70 via the solder ball 60 (connection material) on the second main surface side of the solid-state image sensor substrate 100.

FIG. 2 is an enlarged cross-sectional view showing the solid-state imaging element substrate 100 of FIG. 1.

The solid-state imaging device substrate 100 includes the following components: a germanium substrate 10 as a substrate, an image sensor 12, an interlayer insulating film 13, a base layer 14, a red color filter 15R, a green color filter 15G, and blue. The color filter 15B, the protective layer 16, the microlens 17, the light shielding film 18, the insulating film 22, the metal electrode 23, the solder resist layer 24, the internal electrode 26, and the element surface electrode 27.

However, the solder resist layer 24 can also be omitted.

First, the configuration of the first main surface side of the solid-state imaging device substrate 100 will be mainly described.

As shown in FIG. 2, a plurality of charge coupled devices (CCDs) or complementary metal oxide semiconductors (Complementary Metal Oxide) are provided on the first main surface side of the germanium substrate 10 as a substrate of the solid-state image sensor substrate 100. An imaging element unit in which the imaging elements 12 such as Semiconductor, CMOS) are two-dimensionally arranged.

An interlayer insulating film 13 is formed on the image pickup element 12 in the image pickup element portion, and a base layer 14 is formed on the interlayer insulating film 13. Further, a red color filter 15R, a green color filter 15G, and a blue color filter 15B are disposed on the base layer 14 so as to correspond to the image sensor 12 (hereinafter, sometimes These color filters are collectively referred to as "color filters 15").

A light shielding film (not shown) may be provided at a boundary portion between the red color filter 15R, the green color filter 15G, and the blue color filter 15B, and the periphery of the imaging element portion. This light-shielding film can be produced, for example, using a well-known black color resist.

A protective layer 16 is formed on the color filter 15, and a microlens 17 is formed on the protective layer 16 so as to correspond to the image pickup element 12 (color filter 15).

Further, a peripheral circuit (not shown) and an internal electrode 26 are provided around the imaging element portion on the first main surface side, and the internal electrode 26 is electrically connected to the imaging element 12 via a peripheral circuit.

Further, on the internal electrode 26, the element surface electrode 27 is formed via the interlayer insulating film 13. A contact plug (not shown) that electrically connects the electrodes is formed in the interlayer insulating film 13 between the internal electrode 26 and the element surface electrode 27. The element surface electrode 27 is used for voltage application, signal reading, and the like via the contact plug and the internal electrode 26.

A base layer 14 is formed on the element surface electrode 27. A protective layer 16 is formed on the base layer 14. The base layer 14 and the protective layer 16 formed on the element surface electrode 27 are opened to form a pad opening, thereby exposing a part of the element surface electrode 27.

The above is the configuration of the first main surface side of the solid-state imaging device substrate 100.

On the first main surface side of the solid-state imaging device substrate 100, an adhesive 20 is provided around the imaging element portion, and the solid imaging device substrate 100 and the glass substrate 30 are adhered via the adhesive 20.

Further, the ruthenium substrate 10 has a through hole penetrating the ruthenium substrate 10, and a through electrode as a part of the metal electrode 23 is provided in the through hole. The imaging element portion is electrically connected to the circuit board 70 by the through electrode.

Next, the configuration of the second main surface side of the solid-state imaging device substrate 100 will be mainly described.

On the second main surface side, an insulating film 22 is formed on the second main surface over the inner wall of the through hole.

A patterned metal electrode 23 is provided on the insulating film 22 so as to extend from the region on the second main surface of the substrate 10 to the inside of the through hole. The metal electrode 23 is an electrode for connecting the imaging element portion and the circuit substrate 70 in the solid-state imaging device substrate 100.

The through electrode is a portion of the metal electrode 23 that is formed inside the through hole. The through electrode penetrates a part of the germanium substrate 10 and the interlayer insulating film to reach the lower side of the internal electrode 26, and is electrically connected to the internal electrode 26.

Further, a solder resist layer 24 (protective insulating film) is provided on the second main surface side, and the solder resist layer 24 covers the second main surface on which the metal electrode 23 is formed, and has a part of the metal electrode 23 exposed. The opening.

Further, a light shielding film 18 is provided on the second main surface side, and the light shielding film 18 covers the second main surface on which the solder resist layer 24 is formed, and has an opening portion for exposing a part of the metal electrode 23.

In this configuration, (1) the light-shielding solder resist layer in which the light-shielding film 18 and the solder resist layer 24 are a single layer may be formed of the composition of the present invention, or (2) the light-shielding film 18 The solder resist layer 24 is a different layer, and the light shielding film 18 can be formed of the composition of the present invention (in this case, the solder resist layer can be formed of a known solder resist composition).

In FIG. 2, the light-shielding film 18 is patterned so as to cover a part of the metal electrode 23 and expose the remaining portion. However, it is also possible to pattern the metal electrode 23 so as to be entirely exposed (solder resist). The same is true for the patterning of layer 24.

Further, the solder resist layer 24 may be omitted, or the light shielding film 18 may be directly formed on the second main surface on which the metal electrode 23 is formed.

A solder ball 60 as a connection member is provided on the exposed metal electrode 23, and the metal electrode 23 of the solid-state image sensor substrate 100 is electrically connected to a connection electrode (not shown) of the circuit board 70 via the solder ball 60.

The configuration of the solid-state imaging device substrate 100 has been described above. However, in the solid-state imaging device substrate 100, the portions other than the light-shielding film 18 can be used by the Japanese Patent Laid-Open Publication No. 2009-158863, paragraph number 0033 to paragraph 0068. The method described in the above, or a known method such as the method described in paragraphs 0036 to 0065 of JP-A-2009-99591, is known.

The light shielding film 18 can be formed by the above-described method for producing a light shielding film of the present invention.

The interlayer insulating film 13 can be formed, for example, by sputtering, chemical vapor deposition (CVD), or the like as an SiO ₂ film or a SiN film.

The color filter 15 uses, for example, a known color resist, and is made of light. The lithography is formed.

As the protective layer 16 and the base layer 14, for example, a known resist for forming an organic interlayer film is used, and is formed by photolithography.

The microlens 17 is formed by, for example, photolithography using a styrene resin or the like.

When the solder resist layer 24 and the light shielding film 18 are combined to form a single layer of the light-shielding solder resist layer, the layer is preferably formed of the composition of the present invention.

On the other hand, when the solder resist layer 24 and the light shielding film 18 are different layers, the solder resist layer 24 preferably uses, for example, a known solder resist containing a phenol resin, a polyimide resin, or an amine resin. Formed by light lithography.

The solder ball 60 is formed using, for example, Sn-Pb (eutectic), 95Pb-Sn (high-lead high-melting solder), Sn-Ag, Sn-Cu, Sn-Ag-Cu, or the like as a Pb-free solder. The solder ball 60 is formed, for example, in a spherical shape having a diameter of 100 μm to 1000 μm (preferably, a diameter of 150 μm to 700 μm).

The internal electrode 26 and the element surface electrode 27 are formed as a metal electrode of Cu or the like by, for example, chemical mechanical polishing, photolithography, and etching.

The metal electrode 23 is formed as a metal electrode such as Cu, Au, Al, Ni, W, Pt, Mo, a Cu compound, a W compound, or a Mo compound by sputtering, photolithography, etching, or electrolytic plating. . The metal electrode 23 may be composed of a single layer or may have a laminated structure including two or more layers. The film thickness of the metal electrode 23 is, for example, 0.1 μm to 20 μm (preferably 0.1 μm to 10 μm). The germanium substrate 10 is not particularly limited. However, a tantalum substrate which is thinned by cutting off the back surface of the substrate can be used. The thickness of the substrate is not limited, and for example, a tantalum wafer having a thickness of 20 μm to 200 μm (preferably 30 μm to 150 μm) is used.

The through hole of the ruthenium substrate 10 is formed, for example, by photolithography and reactive ion etching (RIE).

Although the solid-state imaging device substrate 100 as a specific example of the above-described embodiment has been described above with reference to FIG. 1 and FIG. 2, the above-described embodiment is not limited to the embodiment of FIGS. 1 and 2, and is provided with a metal electrode on the back side. The configuration of the light shielding film is not particularly limited.

Next, an example in which a permanent pattern obtained from the composition of the present invention is applied to a light-shielding film of a wafer-level lens will be described with reference to the drawings.

7 is a plan view showing an example of a configuration of a wafer level lens array having a plurality of wafer level lenses.

As shown in FIG. 7, the wafer level lens array includes a substrate 410 and a lens 412 arranged on the substrate 410. Here, in FIG. 7, the plurality of lenses 412 are two-dimensionally arranged with respect to the substrate 410, but the plurality of lenses 412 may be arranged one-dimensionally.

In addition, FIG. 8 is a cross-sectional view taken along line A-A shown in FIG.

As shown in FIG. 8, in the wafer level lens array, a light shielding film 414 that prevents light from passing through a portion other than the lens 412 is provided between the plurality of lenses 412 arranged on the substrate 410.

The wafer level lens includes one lens 412 existing on the substrate 410 and a light shielding film 414 provided on the peripheral portion thereof. The composition of the present invention can be used for the light shielding film Formation of 414.

Hereinafter, a configuration of a wafer-level lens array in which a plurality of lenses 412 are two-dimensionally arranged with respect to the substrate 410 as shown in FIG. 7 will be described as an example.

The lens 412 generally comprises the same material as the substrate 410, which is integrally formed on the substrate 410 or formed as another structure and then fixed on the substrate. Although an example is given here, the wafer-level lens of the present invention is not limited to this embodiment, and various forms such as a wafer-level lens having a multilayer structure and being separated into a lens module by dicing may be employed. Wafer level lens.

As a material which forms the lens 412, glass is mentioned, for example. There are many types of glass, and those having a high refractive index can be selected, and thus are suitable for materials having a lens having high power. Further, the glass is also excellent in heat resistance and can withstand the reflow mounting of an image pickup unit or the like.

As another material which forms the lens 412, a resin is mentioned. The resin is excellent in workability, and is suitable for forming a lens surface easily and inexpensively by a mold or the like.

In this case, when forming the lens 412, it is preferred to use an energy curable resin. The energy curable resin may be either a resin that is cured by heat or a resin that is cured by irradiation with an active energy ray (for example, heat, ultraviolet rays, or electron beam irradiation).

Any of the known resins may be used as the energy curable resin. However, in consideration of reflow mounting of the image pickup unit, it is preferable that the softening point is, for example, a resin having a relatively high softening point such as 200 ° C or higher, and more preferably a softening point of 250. Resin above °C.

Hereinafter, the form and production of the wafer level lens will be described with reference to FIGS. 9 to 14 . A method of fabricating a wafer level lens array will be specifically described as an example.

[Formation and Fabrication of Wafer Level Lens (1)]

- Formation of the lens -

First, a method of forming the lens 412 on the substrate 410 will be described with reference to FIGS. 9 and 10(A) to 10(C).

Here, FIG. 9 is a view showing a state in which a molding material (described as M in FIG. 9) as a resin composition for forming a lens is supplied onto the substrate 410.

10(A) to 10(C) are diagrams showing a procedure for molding the lens 412 on the substrate 410 by the mold 460.

As shown in FIG. 9, the forming material M is dropped onto the portion of the substrate 410 where the lens 412 is shaped using the dispenser 450. Here, the molding material M corresponding to the amount of one lens 412 is supplied to one of the supplied portions.

After the molding material M is supplied onto the substrate 410, as shown in FIG. 10(A), a mold 460 for molding the lens 412 is disposed on the surface side of the substrate 410 on which the molding material M is supplied.

Here, in the mold 460, a recess 462 having a shape to transfer the lens 412 is provided corresponding to the number of the desired lenses 412.

As shown in FIG. 10(B), the mold 460 is pressed against the molding material M on the substrate 410, and the molding material M is deformed in accordance with the shape of the concave portion 462. In the state in which the mold 460 is pressed against the molding material M, when the molding material M is a thermosetting resin or an ultraviolet curable resin, heat or ultraviolet rays are irradiated from the outside of the mold 460 to cure the molding material M.

After the molding material M is cured, as shown in FIG. 10(C), the substrate 410 and the lens 412 are released from the mold 460.

- Formation of light shielding film -

Next, a method of forming the light shielding film 414 on the peripheral portion of the lens 412 will be described with reference to FIGS. 11(A) to 11(C).

Here, FIGS. 11(A) to 11(C) are schematic cross-sectional views showing a step of providing a light shielding film 414 on the substrate 410 on which the lens 412 is formed.

The method of forming the light-shielding film 414 includes a step of forming a light-shielding coating layer on which the composition of the present invention is applied onto the substrate 410 to form the light-shielding coating layer 414A (see FIG. 11(A)); The light-shielding coating layer 414A performs an exposure step of pattern exposure (see FIG. 11(B)); and develops the exposed light-shielding coating layer 414A to remove the uncured portion to form a patterned light-shielding film 414. Development step (refer to Fig. 11 (C)).

Further, the formation of the light shielding film 414 may be performed before the lens 412 is formed, or may be performed after the lens 412 is formed. Here, the method of fabricating the lens 412 will be described in detail.

Hereinafter, each step in the method of forming the light shielding film 414 will be described.

<Light-shielding coating layer forming step>

In the light-shielding coating layer forming step, as shown in FIG. 11(A), a composition is applied onto the substrate 410 to form a light-shielding coating layer 414A having a low light reflectance of the composition. At this time, the light-shielding coating layer 414A is a surface that covers the entire surface of the substrate 410 and the lens surface 412a of the lens 412 and the surface of the lens edge portion 412b. Formed.

The substrate 410 which can be used in this step is not particularly limited. For example, sodium glass, an alkali-free glass, pyrex (registered trademark) glass, quartz glass, a transparent resin, etc. are mentioned.

In addition, the substrate 410 described herein is a form in which the lens 412 and the substrate 410 are integrally formed, and includes a form including both the lens 412 and the substrate 410.

Further, in order to improve the adhesion to the upper layer, prevent the diffusion of the substance, or to planarize the surface of the substrate 10, an undercoat layer may be provided on the substrates 410 as needed.

As a method of coating the composition on the substrate 410 and the lens 412, various coating methods such as slit coating, spray coating, inkjet method, spin coating, cast coating, roll coating, and screen printing can be applied. .

The film thickness immediately after application of the composition is preferably from 0.1 μm to 10 μm, more preferably from 0.2 μm to 5 μm, from the viewpoint of uniformity of film thickness of the coating film and ease of drying of the coating solvent. More preferably, it is 0.2 μm to 3 μm.

The drying (prebaking) of the light-shielding coating layer 414A applied to the substrate 410 can be carried out at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds using a hot plate, an oven or the like.

The thickness of the coating film after drying of the composition (hereinafter, referred to as "dry film thickness" as appropriate) can be arbitrarily selected depending on properties such as desired light blocking properties, and is approximately 0.1 μm or more and less than 50 μm.

<Exposure step>

In the exposure step, the light-shielding coating layer 414A formed in the light-shielding coating layer forming step is exposed in a pattern. The pattern exposure may be a scanning exposure, but it is preferably a form in which exposure is performed through a mask 70 having a predetermined mask pattern as shown in FIG. 11(B).

In the exposure in this step, the pattern exposure of the light-shielding coating layer 414A is performed by a predetermined mask pattern, and only the portion of the light-shielding coating layer 414A that is irradiated with light is cured by the exposure. Here, a mask pattern that illuminates the surface of the substrate 410 between the surface of the lens edge portion 412b and the lens 412 is used. Thereby, only the light-shielding coating layer 414A in the region other than the lens surface 412a is cured by light irradiation, and the hardened region forms the light shielding film 414.

As the radiation which can be used for exposure, ultraviolet rays such as g-rays, h-rays, and i-rays can be preferably used. The radiation may be a single wavelength source, or a source of all wavelengths such as a high pressure mercury lamp.

<Development step>

Then, by performing an alkali development treatment (development step), the unexposed portion of the light that is not irradiated, that is, the uncured region of the light-shielding coating layer 414A is eluted into the alkaline aqueous solution, and only the region hardened by the light irradiation remains. .

Specifically, the light-shielding coating layer 414A which has been exposed as shown in FIG. 11(B) is developed, whereby only the light-shielding coating formed on the lens surface 12a is applied as shown in FIG. 11(C). The cloth layer 414A is removed, and a hardened light-shielding film 414 is formed in a region other than the cloth layer 414A.

Contained as a developing solution (alkaline aqueous solution) used in the developing step As the alkali agent, an organic or inorganic alkali agent and any combination of these may be used. In the case of forming the light-shielding film of the present invention, it is difficult to damage the surrounding circuit or the like, and it is preferable to use an organic alkali agent.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1, An organic basic compound (organic alkali agent) such as 8-diazabicyclo-[5,4,0]-7-undecene, an inorganic compound such as sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate or potassium hydrogencarbonate ( The inorganic alkali agent or the like is preferably used as a developing solution to dilute the alkaline agent by using pure water so as to have a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass. An alkaline aqueous solution.

The development temperature is usually 20 ° C to 30 ° C, and the development time is in the range of 20 seconds to 90 seconds.

In addition, when a developing solution containing such an alkaline aqueous solution is used, the unexposed portion of the coating film is usually removed by a developing solution, and then washed (washed) with pure water. That is, after the development treatment, the remaining developer is sufficiently washed and removed with pure water, and the drying step is further carried out.

Furthermore, after the light-shielding coating layer forming step, the exposing step, and the developing step, the light-shielding film (light-shielding pattern) formed by heating (post-baking) and/or exposure may be included as needed. A hardening step of hardening is performed.

The post-baking is a heat treatment after development for achieving complete hardening, and is usually performed by a heat hardening treatment at 100 ° C to 250 ° C. Conditions such as temperature and time of post-baking can be appropriately set depending on the material of the substrate 410 or the lens 412. For example, when the substrate 412 In the case of glass, it is preferable to use 180 ° C to 240 ° C among the above temperature ranges.

The heating means such as a hot plate or a convection oven (hot air circulation dryer) or a high-frequency heating machine can be used to perform the above-described conditions, and the light-shielding film 414 formed after development can be subjected to continuous or batch type. Post-baking treatment.

In the above procedure, the case where the shape of the lens 412 is concave is described as an example, but the shape is not particularly limited, and may be a convex or aspherical shape. Further, in the above-described procedure, a wafer-level lens in which a plurality of lenses 412 are formed on one surface of the substrate 410 has been described as an example. However, a plurality of lenses 412 may be formed on both surfaces of the substrate 410. In this case, a pattern-like light-shielding film 414 is formed on the two surfaces in a region other than the lens surface.

[Formation and Fabrication of Wafer Level Lens (2)]

Fig. 12 is a view showing another configuration example of a wafer level lens array. The wafer level lens shown in FIG. 12 is a configuration (monolithic type) in which the substrate 410 and the lens 412 are simultaneously molded by the same molding material.

When such a wafer level lens is produced, the same material as the above-mentioned molding material can be used as the molding material. Further, in this example, a plurality of concave lenses 412 are formed on one surface (the upper surface in the drawing) of the substrate 410, and a plurality of convex shapes are formed on the other surface (the lower surface in the drawing). Lens 420. Further, a pattern-shaped light-shielding film 414 is formed on a surface of the substrate 410 other than the lens surface 412a, that is, on the surface of the substrate 410 and the surface of the lens edge portion 412b. As the patterning method at the time of forming the light shielding film 414, the above procedure can be applied.

[Formation and Fabrication of Wafer Level Lens (3)]

Next, another configuration example of the wafer level lens array and a program for creating another configuration example will be described with reference to FIGS. 13(A) to 13(C) and FIGS. 14(A) to 14(C).

Here, FIGS. 13(A) to 13(C) are schematic views showing other steps of forming the patterned light shielding film 414.

14(A) to 14(C) are schematic views showing a procedure of first forming a pattern-shaped light-shielding film 414 and then molding the lens 412.

An example of the wafer-level lens array shown in FIGS. 9 to 12 is an example in which a patterned light-shielding film 414 is formed on a substrate 410 on which a lens 412 is provided. However, the procedure described below first forms a pattern on the substrate 410. The light-shielding film 414 is then subjected to a process of forming the lens 412 on the substrate 410.

- Formation of light shielding film -

First, as shown in FIG. 13(A), a light-shielding coating layer forming step of applying a composition onto the substrate 410 to form the light-shielding coating layer 414A is performed.

Thereafter, the light-shielding coating layer 414A applied to the substrate 410 is dried at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds using a hot plate or an oven. The dry film thickness of the composition can be arbitrarily selected in accordance with properties such as desired light blocking properties, and is approximately 0.1 μm or more and less than 50 μm.

Then, as shown in FIG. 13(B), an exposure step of exposing the light-shielding coating layer 414A formed in the light-shielding coating layer forming step to a pattern is performed through the mask 470. The mask 470 has a prescribed mask pattern.

In the exposure in this step, the light-shielding coating layer 414 is patterned. By this, only the portion of the light-shielding coating layer 414A that is irradiated with light is hardened. Here, a mask pattern that irradiates light only to the light-shielding coating layer 414A in the following region is used: a region other than the portion of the lens opening 414a of the lens 412 when the lens 412 is formed in the subsequent step. According to this method, only the light-shielding coating layer 414A in the region other than the portion of the lens opening 414a of the lens 412 is cured by light irradiation. Further, as the radiation which can be used for exposure, ultraviolet rays such as g-rays, h-rays, and i-rays can be preferably used in the same manner as the procedure described above.

Then, an alkali development treatment (development step) is performed, whereby only the light-shielding coating layer 414A in the following region is eluted to the alkaline aqueous solution: the lens 412 of the uncured region which is the light-shielding coating layer 414A in the above-described pattern exposure The area corresponding to the lens opening 414a. At this time, as shown in FIG. 13(C), the light-curable light-shielding coating layer 414A in the region other than the region of the lens opening 414a of the lens 412 remains on the substrate 410, and the light-shielding film 414 is formed.

Here, as the alkali agent in the alkaline aqueous solution of the developer, the same alkali agent as the procedure described above can be used. After the development treatment, the remaining developer is then washed and removed, and dried.

In the present embodiment, after the light-shielding coating layer forming step, the exposing step, and the developing step are performed, the formed light-shielding film may be cured by the post-baking and/or exposure as necessary. Hardening step.

When the composition of the present invention is attached to, for example, a nozzle of a coating apparatus discharge unit, a piping unit of a coating apparatus, a coating apparatus, or the like, it can be easily removed by washing using a known cleaning liquid. In this case, in order to be more efficient For the cleaning and removal, it is preferred to use the solvent disclosed as the solvent contained in the composition of the present invention as a cleaning liquid.

In addition, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The cleaning liquid described in the Japanese Patent Laid-Open Publication No. Hei. No. 2007-281523, the Japanese Patent Publication No. 2007-2102, and the Japanese Patent Publication No. 2007-281523, and the like can also be used. It is suitably used as a cleaning liquid for cleaning and removal of the composition of the present invention.

As the cleaning liquid, an alkylene glycol monoalkyl ether carboxylate or an alkylene glycol monoalkyl ether is preferably used.

These solvents which can be used as the cleaning liquid can be used singly or in combination of two or more.

When two or more solvents are mixed, a mixed solvent obtained by mixing a solvent having a hydroxyl group and a solvent having no hydroxyl group is preferred. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. As a mixed solvent, particularly preferred is a ratio of 60/40 propylene glycol monomethyl ether acetate (PGMEA; alias 1-methoxy-2-ethoxypropane propane) and propylene glycol monomethyl ether (PGME; alias 1-A A mixed solvent of oxy-2-propanol).

Further, in order to enhance the permeability of the cleaning liquid to the composition, the surfactant disclosed as the surfactant which can be contained in the composition may be added to the cleaning liquid.

- Formation of the lens -

Next, a step of forming the lens 412 after forming the light shielding film 414 will be described.

As shown in FIG. 14(A), the molding material M constituting the lens 412 is dropped onto the substrate 410 on which the patterned light shielding film 414 is formed by the dispenser 450. In order to cover a region corresponding to the lens opening 414a of the lens 412, the molding material M is supplied in such a manner as to include a part of the end portion of the light shielding film 414 adjacent to the opening.

After the molding material M is supplied onto the substrate 410, as shown in FIG. 14(B), a mold 480 for molding the lens is disposed on the surface side of the substrate 410 on which the molding material M is supplied. In the mold 480, a recess 482 having a shape to transfer the lens 412 is provided corresponding to the number of lenses 412 desired.

The mold 480 is pressed against the molding material M on the substrate 410, and the molding material M is deformed in accordance with the shape of the concave portion. Further, in a state where the mold 480 is pressed against the molding material M, when the molding material M is a thermosetting resin or an ultraviolet curable resin, heat or ultraviolet rays are irradiated from the outside of the mold, whereby the molding material M is cured.

After the molding material M is cured, the substrate 410 and the lens 412 are released from the mold 480, and as shown in FIG. 14(C), a wafer-level lens having a patterned light-shielding film 414 on the substrate 410 is obtained.

As described above, the pattern-shaped light-shielding film 414 provided in the wafer-level lens is not only provided in a region other than the lens surface 412a of the lens 412 as shown in FIG. 11, but also as shown in FIG. 14(C). In order to dispose the light shielding film 414 in the lens 412 The configuration of the region other than the lens opening 414a.

The wafer-level lens is sufficiently shielded from the lens surface 412a of the lens 412 or a region other than the lens opening 414a by forming a light-shielding film 414 having a low light reflectance in a pattern on at least one surface of the substrate 410, and suppresses reflection. The generation of light. Therefore, when applied to an image pickup module including a solid-state image sensor, it is possible to prevent occurrence of problems such as ghost or flare of the reflected light during image pickup.

Further, since the light shielding film 414 is provided on the surface of the substrate, it is not necessary to mount another light shielding member or the like in the wafer level lens, and an increase in manufacturing cost can be suppressed.

In the case where the structure having the surface unevenness is provided around the lens, it is feared that light reflected or diffused into the structure is likely to cause problems such as ghosting. Therefore, if the patterned light-shielding film 414 is provided in a region other than the lens surface 412a of the lens 412 as shown in FIG. 11, the light can be shielded outside the lens surface 412a, and the optical performance can be improved.

Example

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the following examples as long as the scope of the invention is not exceeded. In addition, "parts" and "%" are quality standards unless otherwise specified.

<Preparation of Filler Dispersion 1>

In advance, cerium oxide filler (manufactured by Aerosil (Japan), Aerosil 50 particle size: 30 nm) 6.8 parts by mass, alkali-soluble resin (ACA230AA, Daicel-Cytec (share), Weight average molecular weight is 14,000 (by gel permeation chromatography (Gel Permeation) Chromatography (GPC) obtained by polystyrene conversion), solid content: 50% by mass, solvent: propylene glycol monomethyl ether acetate (PGME)) 92.9 parts by mass, and melamine 0.3 parts by mass after mixing, by motor mill (motor mill) M-50 (manufactured by Eiger), and zirconia beads having a diameter of 1.0 mm were used, and dispersed at a peripheral speed of 9 m/s for 1.5 hours. The filler dispersion 1 was prepared by filtration using a Profile Star (polypropylene filtration precision: 1.5 μm) manufactured by Pall, Japan.

<Preparation of solder resist composition>

(Example 1)

The following composition was mixed, and filtration was carried out using HDCII (high-density polypropylene filtration precision: 6.0 μm) manufactured by Pall Japan, and the composition of Example 1 was obtained. The solid content concentration of the composition of Example 1 was 47% by mass. The viscosity is 300mPa. s.

. Infrared opaque particle YMF-02 (a 18.5 mass% dispersion of 铯tungsten oxide (Cs _0.33 WO ₃ , particle size of the maximum value in particle size distribution: 20 nm) manufactured by Sumitomo Metal Mine Co., Ltd.) 19.13 parts by mass

. Polymerizable compound Compound D: diglycerin EO modified (meth) acrylate (manufactured by Toagosei Co., Ltd., M-460) 4.63 parts by mass

. Polymerization initiator α-amino ketone polymerization initiator (Compound A), IRGACURE 369 (manufactured by BASF Corporation) 1.10 parts by mass

. Sensitizer Kayacure DETX-S (thiaxanthone compound manufactured by Nippon Kayaku Co., Ltd.) 0.38 parts by mass

. UV absorber DPO (manufactured by Fujifilm Fine Chemicals) 0.07 parts by mass

. Decane coupling agent KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) 2.10 parts by mass

. Surfactant Megafac F-780 (manufactured by Di Ai Sheng Co., Ltd.) 0.10 parts by mass

. The above filler dispersion 1 58.39 parts by mass

. Solvent PGMEA 14.10 parts by mass

(Example 2 to Example 3)

The composition of Example 2 and Example 3 was obtained by the same composition as that of Example 1 except that the photopolymerization initiator (Compound A) was replaced with the above-mentioned Compound B and Compound C. The solid content concentrations of the compositions of Example 2 and Example 3 were respectively 47% by mass. The composition of Example 2 has a viscosity of 200 mPa. s, the composition of Example 3 has a viscosity of 200 mPa. s.

Compound B lanthanide polymerization initiator, IRGACURE OXE01 (manufactured by BASF Corporation)

Compound C triazine polymerization initiator (synthesized according to a known method)

(Comparative Example 1 to Comparative Example 4)

In addition to replacing compound D of Example 1 with compound E~ compound Other than H, the composition of Comparative Example 1 to Comparative Example 4 was obtained by setting the same composition as in Example 1. The solid content concentrations of the compositions of Comparative Examples 1 to 4 were 47% by mass.

Compound E dipentaerythritol hexaacrylate (synthesized according to a known method)

Compound F manufactured by Nippon Kayaku, KAYARAD DPHA (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)

Compound G manufactured by Nippon Kayaku, KAYARAD PR-1040

Compound H Xinzhongcun Chemical Manufacturing A-DPH-12E (EO modified dipentaerythritol hexaacrylate)

(Comparative Example 5)

The infrared light-shielding particle (YMF-02) of Example 1 was replaced with the following carbon black dispersion liquid H, and the input amount was changed from 19.13 parts by mass to 30.27 parts by mass, and the solvent (PGMEA) input amount was replaced with 14.10 parts by mass. The composition of Comparative Example 5 was obtained by the same composition as in Example 1 except that the composition was the same as that of the above. The solid content concentration of the composition of Comparative Example 5 was 47% by mass.

(Preparation of carbon black dispersion H)

The following composition I was subjected to a high viscosity dispersion treatment using a two-roll mill to obtain a dispersion. Thereafter, a mixture of the following composition II was added to the dispersion, and the mixture was stirred at 3000 rpm for 3 hours using a homogenizer. The obtained mixed solution was carried out by using a dispersing machine of zirconia beads having a particle size of 0.3 mm (trade name: Dispermat, manufactured by GETZMANN). The carbon black dispersion (solid content concentration: 18.0% by mass) was prepared by microdispersion treatment in an hour.

(composition I)

. Carbon black (Pigment Black 7) having a particle size of 15 nm indicating a maximum value in the particle size distribution 23 parts by mass

. 45 mass% solution of PGMEA of benzyl methacrylate/methacrylic acid copolymer (copolymerization ratio of benzyl methacrylate/methacrylic acid=67/33 (mol%), Mw: 28000) 22 parts by mass

. Solsperse5000 (made by Lubrizol, Ltd.) 1.2 parts by mass

(composition II)

. 45 mass% solution of PGMEA of benzyl methacrylate/methacrylic acid copolymer (benzyl methacrylate unit / methacrylic acid unit = 67/33 (mol%), Mw: 28000) 22 parts by mass

. PGMEA 176 parts by mass

<Evaluation of solder resist composition>

(infrared opacity)

The composition was spin-coated on a glass substrate under the above conditions to form a coating film of a photosensitive layer (solder resist composition layer) having a film thickness of 25 μm, and the coating was measured using an ultraviolet-visible near-infrared spectrophotometer UV 3600 (manufactured by Shimadzu Corporation). The transmittance of the film at a wavelength of 1200 nm. The lower the transmittance, the more excellent the infrared shielding property. The evaluation was performed based on the following evaluation criteria.

[evaluation benchmark]

5: The transmittance is 2% or less.

4: The transmittance is greater than 2% and is 3% or less.

3: The transmittance is more than 3% and less than 5%.

2: The transmittance is more than 5% and less than 10%.

1: The transmission rate is greater than 10%.

(time residue)

Each of the obtained infrared ray compositions was stored in a refrigerator (4° C.) for 6 months, and then each of the infrared ray compositions was applied to a ruthenium wafer by a spin coating method so that the film thickness became 25 μm. Thereafter, The photosensitive layer was obtained by heating at 120 ° C for 2 minutes on a hot plate.

Then, using an i-ray stepper, the exposure amount in the range of 50 mJ/cm ² to 2000 mJ/cm ² was changed by 50 mJ/cm ² each time through a photomask having a pattern having a diameter of 300 μm. The photosensitive layer is irradiated.

The exposed photosensitive layer was subjected to puddle development for 40 seconds at 25 ° C using a tetramethylammonium hydroxide 2.38 mass% aqueous solution. Thereafter, it was rinsed by spin spraying, and further washed with pure water to obtain an infrared shielding resist pattern. The inside of the pattern of a circle having a diameter of 300 μm obtained when the development step was performed for 60 seconds was observed with a scanning electron microscope, and evaluated according to the evaluation criteria, and classified by a five-stage evaluation of 5 to 1 by the following evaluation criteria. Level 3 or above is a practical level.

[evaluation benchmark]

5: No roughness was observed on the surface of the substrate, and the level of the residue was not observed at all.

4: No roughness was observed on the surface of the substrate, and the level of the residue was not substantially observed.

3: The roughness was slightly observed on the surface of the substrate, but the residue was within the allowable level.

2: Most of the surface of the substrate is rough and unqualified.

1: Large roughness was observed on the surface of the entire ruthenium substrate, development was incomplete, and the level of failure was unacceptable.

(Time-lapse exposure sensitivity)

Each of the obtained compositions was stored in a refrigerator (4 ° C) for 6 months, and then each composition was applied to a tantalum wafer by a spin coating method so that the film thickness became 25 μm, and then heated. The plate was heated at 120 ° C for 2 minutes to obtain a photosensitive layer.

Then, using an i-ray stepper, the exposure amount in the range of 50 mJ/cm ² to 2000 mJ/cm ² was changed by 50 mJ/cm ² each time through a photomask having a pattern having a diameter of 300 μm. The photosensitive layer is irradiated.

The exposed photosensitive layer was subjected to a liquid-contact development method at 25 ° C for 40 seconds using a tetramethylammonium hydroxide 2.38 mass% aqueous solution. Thereafter, it was rinsed by spin spraying, and further washed with pure water to obtain an infrared shielding resist pattern. The minimum exposure amount (exposure sensitivity) (mJ/cm ² ) of a pattern of a circle having a diameter of 300 μm was obtained when the development step of 60 seconds was performed.

The smaller the value, the better the pattern exposure sensitivity, and the evaluation was performed according to the following evaluation criteria.

[evaluation benchmark]

5: The minimum exposure amount is 200 mJ/cm ² or less.

4: The minimum exposure amount is more than 200 mJ/cm ² and is 250 mJ/cm ² or less.

3: The minimum exposure amount is more than 250 mJ/cm ² and is 300 mJ/cm ² or less.

2: The minimum exposure amount is more than 300 mJ/cm ² and is 350 mJ/cm ² or less.

1: The minimum exposure is greater than 350mJ/cm ² .

(time uniformity of coating)

Each of the infrared ray compositions was stored in a refrigerator (4 ° C) for 6 months, and then coated on a ruthenium wafer by spin coating at 900 rpm for 25 seconds, and obtained on a hot plate at 120 ° C. The wafer was heated for 2 minutes.

The coating uniformity of the coating film obtained above was visually evaluated, and the classification was performed by a five-stage evaluation of 5 to 1 by the following evaluation criteria. Level 3 or above is a practical level.

[evaluation benchmark]

5: No roughness was observed on the surface, and the level of the coated surface was no problem.

4: The surface was hardly seen to be rough, and the coated surface was substantially level.

3: A part of the surface is rough, and the coated surface is slightly inferior, but it is within the allowable level.

2: Most of the surface is rough, and the coated surface is poor, and the level of failure is unqualified.

1: Roughness was observed on the entire surface, and the coated surface was quite poor, which was unqualified.

As is clear from the above table, it is understood that when a composition containing the compound represented by the formula (1) and the infrared light-blocking particles is used (Examples 1 to 3), the infrared ray opacity is maintained, and The adaptability of the time change becomes excellent. On the other hand, when the composition of the compound similar to the compound D used in the present invention, such as the compound E to the compound H, was used (Comparative Example 1 to Comparative Example 4), although the infrared ray blocking property was maintained, The change over time is remarkable, and the composition after the lapse tends to have a residue falling, or a problem of poor sensitivity or poor coatability.

10‧‧‧矽 substrate

12‧‧‧Photographic components

13‧‧‧Interlayer insulating film

14‧‧‧ base layer

15R‧‧‧Red color filter

15G‧‧‧Green color filter

15B‧‧‧Blue color filter

16‧‧‧Protective layer

17‧‧‧Microlens

18‧‧‧Shade film

20‧‧‧Adhesive

22‧‧‧Insulation film

23‧‧‧Metal electrodes

24‧‧‧ solder resist layer

26‧‧‧Internal electrodes

27‧‧‧Component surface electrode

30‧‧‧ glass substrate

60‧‧‧ solder balls

70‧‧‧ circuit board

100‧‧‧Solid imaging element substrate

Claims (18)

A solder resist composition comprising a compound represented by the general formula (1) and infrared light-shielding particles: In the formula (1), L is a group each containing a combination of an alkylene group and -O-, and each of Ac is a (meth)acryloxy group. The solder resist composition according to claim 1, wherein in the formula (1), L is a group comprising a combination of -C ₂ H ₄ - and -O-. The solder resist composition according to claim 1, wherein in the formula (1), L is a group comprising a combination of -CH ₂ - and -O-. The solder resist composition according to claim 1 or 2, wherein the infrared ray blocking particles comprise a tungsten compound. The solder resist composition according to claim 1 or 2, wherein the infrared ray blocking particles are represented by the following general formula (2): M _x W _y O _z (2) M represents a metal, W Indicates tungsten, O represents oxygen; 0.001 ≦ x / y ≦ 1.1; 2.2 ≦ z / y ≦ 3.0. The solder resist composition according to claim 5, wherein in the formula (2), M is an alkali metal. The solder resist composition according to claim 5, wherein in the formula (2), M is ruthenium. The solder resist composition according to claim 1 or 2, further comprising a polymerization initiator and/or an alkali-soluble binder. The solder resist composition according to claim 8, which further comprises an α-amino ketone polymerization initiator. The solder resist composition according to claim 1 or 2, wherein the solid content concentration is 30% by mass to 80% by mass. A cured film formed by curing a solder resist composition according to any one of claims 1 to 10. A solid-state imaging element comprising the cured film according to claim 11 of the patent application. A liquid crystal display device comprising the cured film according to claim 11 of the patent application. An organic EL display device comprising the cured film according to claim 11 of the patent application. A method of producing a pattern hardening film, comprising: applying a solder resist composition according to any one of claims 1 to 10 to a substrate; and patterning the solder resist composition The steps of exposure. A method of manufacturing a solid-state imaging device, comprising: The step of applying the solder resist composition according to any one of items 1 to 10 to a substrate; and exposing the solder resist composition to the above. A method of manufacturing a liquid crystal display device, comprising: applying a solder resist composition according to any one of claims 1 to 10 to a substrate; and exposing the solder resist composition A step of. A method of manufacturing an organic electroluminescence display device, comprising: applying a solder resist composition according to any one of claims 1 to 10 to a substrate; and forming the solder resist The step of exposing the object.