KR101890633B1 - Resin composition, method for producing cured product, method for producing resin pattern, cured product and optical member - Google Patents

Abstract

(A) a polymer having (a-1) an acid and / or a monomer unit having a group capable of leaving by heat, and (a-2) a monomer unit having a crosslinkable group, (component B) And (C) a solvent. The cured product of the present invention is a cured product obtained by curing the resin composition, and the optical member of the present invention is an optical member obtained by curing the resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a resin composition, a method of producing a cured product, a method of producing a resin pattern, a cured product and an optical member.

The present invention relates to a resin composition, a method for producing a cured product, a method for producing a resin pattern, a cured product and an optical member.

BACKGROUND ART With the development of solid-state image pickup devices and liquid crystal display devices, optical members such as microlenses, optical waveguides, and antireflection films have been widely made by organic materials (resins).

In order to obtain a high refractive index of these optical members, it has been studied to add particles of titanium oxide or the like (JP-A-2006-98985, JP-A-2001-154181, JP-A-2001-117114, See Japanese Patent Application Laid-Open No. 2011-29474 and Japanese Patent Application Laid-Open No. 2003-96400).

As described in Japanese Patent Application Laid-Open Nos. 2006-98985, 2001-154181, 2001-117114, 2011-29474, and 2003-96400, it is preferable that in the resin composition, The larger the amount of particles added, the higher the refractive index can be obtained. However, from the viewpoint of dispersion stability of the particles, since the amount of the particles that can be added to the resin composition is limited, this method can not sufficiently achieve a high refractive index.

On the other hand, as a resin component having a sufficiently high refractive index (for example, a refractive index of 1.7 or more), a sulfur resin has been used in the field of spectacle lenses and the like (for example, Japanese Patent Application Laid-Open No. 2004-310001).

However, in the field of solid-state image pickup devices and liquid crystal display devices, a sulfur resin can not be used from the viewpoint of processability.

An object of the present invention is to provide a resin composition capable of obtaining a cured product having a high refractive index.

It is another object of the present invention to provide an optical member having a high refractive index and excellent mechanical strength obtained by curing the resin composition.

The above problem of the present invention is solved by the means described in the following <1> or <16> - <19>. Are described below together with the preferred embodiments < 2 > to < 15 >.

(Component A) a polymer having (a-1) a monomer unit having an acid and / or a heat-releasing monomer unit and (a-2) a monomer unit having a crosslinking group, (component B) C) a solvent,

<2> (Component D) The resin composition according to the above <1> or <2>, further containing a photo acid generator,

<3> (Component E) The resin composition according to any one of <1> to <3>, further containing a heat crosslinking agent,

<4> (Component F) The resin composition according to any one of <1> to <4>, further containing an alkali-insoluble resin,

<5> The resin composition according to <4>, wherein the component F is an alkali-insoluble resin having a crosslinkable group,

<6> The resin composition according to <5>, wherein the component F has an epoxy group as a crosslinkable group,

<7> The resin composition according to any one of <4> to <6>, wherein the component F is an epoxy resin or an acrylic resin,

<8> The resin composition according to any one of <1> to <8>, wherein the monomer unit having an acid and / or a thermal desorbing group as the component (a-1) is a monomer unit having a carboxyl- The resin composition according to any one of &lt; 1 &gt; to &lt; 7 &

<9> The resin composition according to any one of <1> to <8>, wherein the monomer unit having a crosslinking group (a-2) is a monomer unit having an epoxy group and / or an oxetanyl group The resin composition,

<10> The resin composition according to any one of <1> to <9>, wherein the component B is an inorganic particle,

<11> The resin composition according to <10>, wherein the inorganic particles are metal oxide particles,

<12> The resin composition according to <11>, wherein the inorganic particles are titanium oxide particles,

<13> The resin composition according to any one of <1> to <12>, which is a photosensitive resin composition,

<14> The resin composition according to any one of <1> to <13> which is a positive-working photosensitive resin composition,

<15> The resin composition according to any one of <1> to <14>, which is a resin composition for an optical member,

<16> A process for producing a cured product, which comprises at least the steps (a) to (c)

(a) a coating step of applying the resin composition described in any one of < 1 > to < 15 >

(b) a solvent removing step of removing the solvent from the applied resin composition

(c) a heat treatment step of heat-treating the resin composition from which the solvent has been removed

<17> A resin pattern manufacturing method comprising at least steps (1) to (5) in this order,

(1) a coating step of applying the resin composition described in any one of < 1 > to < 15 >

(2) a solvent removing step for removing the solvent from the applied resin composition

(3) an exposure step of exposing the resin composition from which the solvent has been removed to a patterned image by an actinic ray

(4) a developing step of developing the exposed resin composition with an aqueous developing solution

(5) Heat treatment process for heat-treating the developed resin composition

<18> A method for producing a cured product according to <16> or a cured product obtained by the method for producing a resin pattern described in <17>

<19> An optical member obtained by the method for producing a cured product described in <16> above, or the method for producing a resin pattern described in <17>.

According to the present invention, a resin composition capable of obtaining a cured product having a high refractive index can be provided.

Further, according to the present invention, it is possible to provide an optical member having a high refractive index and excellent mechanical strength, obtained by curing the resin composition.

Hereinafter, the resin composition of the present invention will be described in detail.

In the present invention, the description of "lower limit to upper limit" indicating the numerical value range indicates "lower limit and upper limit" and the description of "upper limit to lower limit" indicates "upper limit or lower limit. That is, a numerical range including an upper limit and a lower limit.

In the present invention, the term "(Component A) a polymer having (a-1) acid or a monomer unit having a group capable of leaving by heat and (a-2) a monomer unit having a crosslinkable group" (A-1) a monomer unit having a group which is cleaved by an acid or heat &quot;, and the like may be simply referred to as a &quot; monomer unit (a-1) &quot;

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

(Resin composition)

Hereinafter, each component constituting the resin composition will be described.

(A) a polymer having (a-1) an acid and / or a monomer unit having a group capable of leaving by heat, and (a-2) a monomer unit having a crosslinkable group, (component B) And (C) a solvent.

The resin composition of the present invention is preferably a photosensitive resin composition. When the resin composition of the present invention is a photosensitive resin composition, it is preferable to contain (Component D) a photoacid generator.

In addition, the resin composition of the present invention is preferably a resin composition having a property of curing in heat. The resin composition of the present invention is particularly preferably a thermosetting or photosensitive resin composition.

The resin composition of the present invention is preferably a positive photosensitive resin composition.

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

The resin composition of the present invention preferably does not contain a 1,2-quinonediazide compound as a photoacid generator which is sensitive to an actinic ray. The 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is necessarily 1 or less.

On the other hand, the (D) photoacid generator used in the present invention acts as a catalyst against the deprotection of an acidic group protected by an acid generated in response to an actinic ray, Contributes to the deprotection reaction, and the quantum yield exceeds 1, for example, becomes a large value such as 10, and a high sensitivity is obtained as a result of so-called chemical amplification.

The resin composition of the present invention is preferably a resin composition for reducing visibility of an optical member such as a microlens, an optical waveguide, an antireflection film, a sealing material for LED and a tip coating material for LED, or a wiring electrode used for a touch panel , And more preferably a resin composition for a micro lens. The composition for reducing the visibility of the wiring electrode used in the touch panel is a composition for a member that reduces the visibility of the wiring electrode used in the touch panel, that is, makes the wiring electrode difficult to see. For example, ITO Tin) electrodes, and the like. The resin composition of the present invention can be suitably used for such applications.

The resin composition of the present invention can increase the proportion of the particles occupied in the obtained cured product by desorbing the acid and / or heat-releasing groups in the component A by post-baking or the like, Is expected to be obtained.

(Component A) A polymer having (a-1) a monomer unit having an acid and / or a thermal-leaving group and (a-2) a monomer unit having a crosslinkable group

The resin composition of the present invention is a resin composition comprising (A) a monomer unit having a (a-1) acid and / or a thermal elimination group (also simply referred to as a " Units. &Lt; / RTI &gt;

The component A is preferably a polymer having no sulfur atom from the viewpoint of processability in the field of solid-state image pickup devices and liquid crystal display devices.

The component A is a polymer comprising a monomer unit having (a-3) an alkali-soluble group and / or a monomer unit having an aromatic ring (a-4) in addition to the monomer units (a- . The component A may contain monomer units (a-5) other than the monomer units (a-1) to (a-4).

The "monomer unit" in the present invention includes not only a constituent unit formed by one molecule of a monomer but also a constituent unit formed by one molecule of a monomer, which is modified by a polymer reaction or the like.

The weight average molecular weight (Mw) of the component A is preferably 3,000 or more, more preferably 5,000 or more, more preferably 10,000 or more, further preferably 1,000,000 or less, more preferably 80,000 or less, desirable. Within the above range, good resolution can be obtained.

The weight average molecular weight is a polystyrene reduced value measured by GPC (gel permeation chromatography). It is preferable to use THF as the solvent and TSKgel SuperHZ3000 and TSKgel SuperHZM-M (all manufactured by Tosoh Corporation) as the column.

The component A is preferably an acrylic polymer.

The "acrylic polymer" in the present invention is a polymer of addition polymerization type and is a polymer containing a monomer unit derived from (meth) acrylic acid or an ester thereof, and is a polymer other than a monomer unit derived from (meth) acrylic acid or an ester thereof And may have a monomer unit, for example, a monomer unit derived from a styrene or a monomer unit derived from a vinyl compound. The component A may also contain a monomer unit derived from (meth) acrylic acid and a monomer unit derived from a (meth) acrylic acid ester.

In the present specification, the "monomer unit derived from (meth) acrylic acid or an ester thereof" is also referred to as "acrylic monomer unit". Further, (meth) acrylic acid is collectively referred to as methacrylic acid and acrylic acid.

Hereinafter, each monomer unit such as the monomer unit (a-1) and the monomer unit (a-2) will be described.

(a-1) a monomer unit having a group which is cleaved by an acid and /

Component A has at least (a-1) an acid unit and / or a monomer unit having a group which is desorbed by heat.

The group which is cleaved by the acid and / or the heat may be a group which desorbs by an acid, contributes to desorption by heat, contributes to desorption by an acid and heat, but may be a group which is desorbed by an acid, It is preferable that the acid is removed by heat and heat.

At least the group which is cleaved by an acid includes, for example, a residue protected by an acid-decomposable group.

From the viewpoints of sensitivity and resolution, it is preferable that the monomer unit (a-1) is a monomer unit (a-1-1) having a carboxyl group or a residue in which the phenolic hydroxyl group is protected with an acid-decomposable group.

When the monomer unit (a-1-1) is contained, the component A is preferably an alkali-insoluble resin which becomes alkali-soluble when the acid-decomposable group in the monomer unit (a-1-1) Do.

In the present invention, &quot; alkali solubility &quot; other than the component F to be described later means that a solution of the compound (resin) is applied on a substrate and heated at 90 DEG C for 2 minutes to form a solution of the compound Means that the dissolution rate of the coating film (thickness 4 占 퐉) with respect to 0.4 wt% tetramethylammonium hydroxide aqueous solution at 23 占 폚 is 0.01 占 퐉 / second or more, and "alkali insoluble" A coating solution (thickness: 4 占 퐉) of the compound (resin) formed by applying the solution of the compound (resin) onto the substrate and heating the mixture at 90 占 폚 for 2 minutes was coated with 0.4 wt% tetramethylammonium hydroxide Refers to a dissolution rate with respect to the aqueous solution of the lockside of less than 0.01 mu m / second, preferably less than 0.005 mu m / second.

[Monomer unit (a-1-1) having a carboxyl group or a residue whose phenolic hydroxyl group is protected with an acid-decomposable group]

It is preferable that the component A has a monomer unit (a-1-1) having a carboxyl group or a residue in which the phenolic hydroxyl group is protected with an acid-decomposable group.

When the component A has the monomer unit (a-1-1), a highly sensitive resin composition can be obtained. The monomer unit in which the carboxyl group has a residue protected by an acid-decomposable group is characterized in that the phenolic hydroxyl group is faster than the monomer unit having a residue protected by an acid-decomposable group. Therefore, when a rapid development is desired, a monomer unit having a residue whose carboxyl group is protected with an acid-decomposable group is preferable. On the contrary, when it is desired to slow the development, it is preferable to use a monomer unit having a residue in which the phenolic hydroxyl group is protected with an acid-decomposable group.

As the acid decomposable group, a 1-ethoxyethyl group or a tetrahydrofuranyl group is particularly preferable, and a tetrahydrofuranyl group is most preferable.

[Monomer unit (a-1-2) having a residue whose carboxyl group is protected with an acid-decomposable group]

- monomer unit having a carboxyl group -

Examples of the monomer unit having a carboxyl group include a monomer unit derived from an unsaturated carboxylic acid having at least one carboxyl group in a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid and an unsaturated tricarboxylic acid.

As the unsaturated carboxylic acid which can be used for obtaining a monomer unit having a carboxyl group, the following can be used. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid which can be used for obtaining a monomer unit having a carboxyl group may be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. Also, the unsaturated polycarboxylic acid may be mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid, and examples thereof include monosaccharide mono (2-acryloyloxyethyl), succinic acid mono Mono (2-acryloyloxyethyl) phthalate mono (2-methacryloyloxyethyl), and the like.

Also, the unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, .

Examples of the unsaturated carboxylic acid include acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester and 4-carboxystyrene.

Among them, from the viewpoint of developability, it is preferable to use acrylic acid, methacrylic acid, anhydride of unsaturated polycarboxylic acid or the like in order to form a monomer unit having a carboxyl group, and acrylic acid or methacrylic acid is more preferably used.

The monomer unit having a carboxyl group may be composed of one kind alone, or may be composed of two or more kinds.

The monomer unit having a carboxyl group may be a monomer unit obtained by reacting a monomer unit having a hydroxyl group with an acid anhydride.

As the acid anhydride, known dicarboxylic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and anhydrous chloric anhydride; Acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride and biphenyltetracarboxylic anhydride. Of these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride are preferable from the viewpoint of developability.

The reaction ratio of the acid anhydride to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, from the viewpoint of developability.

- monomer unit (a-1-2) having a carboxyl group protected with an acid-decomposable group -

The monomer unit (a-1-2) in which the carboxyl group has a moiety protected with an acid-decomposable group is preferably a monomer unit in which the carboxyl group of the monomer unit having a carboxyl group is a monomer having a moiety protected by an acid- Unit.

As the acid decomposable group, there can be used any known acid decomposable group in the positive resist for KrF and the positive resist for ArF, and there is no particular limitation. Conventionally, as the acid decomposable group, a group which is relatively easily decomposed by an acid, such as an acetal functional group such as a tetrahydropyranyl group, and a group which is relatively difficult to decompose by an acid, such as a t-butyl ester group and a t-butylcarbonate group t-butyl functional groups are known, and they can be used.

These acetal-based functional groups, t-butyl-based functional groups, and ketal based functional groups described below are functional groups capable of causing desorption even by heat.

Among these acid decomposable groups, from the viewpoints of sensitivity and resolution, it is preferable that the carboxyl group is a monomer unit having an acetal-protected residue or a carboxyl group-retained moiety. Among the acid decomposable groups, it is more preferable that the carboxyl group is an acetal or ketal-protected residue represented by the following formula (a1-1). When the carboxy group is an acetal or ketal-protected residue represented by the following formula (a1-1), the moiety has a structure of -C (= O) -O-CR ¹ R ² (OR ³ ) have.

(In the formula (a1-1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, provided that when R ¹ and R ² together are a hydrogen atom, R ³ represents an alkyl group R ¹ or R ² and R ³ may be connected to form a cyclic ether, and the broken line indicates the bonding position with other structures)

In formula (a1-1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, R ³ represents an alkyl group, and the alkyl group may be any of linear, branched and cyclic. Here, both of R ¹ and R ² do not represent a hydrogen atom, and at least one of R ¹ and R ² represents an alkyl group.

In the formula (a1-1), when R ¹ , R ² and R ³ represent an alkyl group, the alkyl group may be any of linear, branched or cyclic.

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

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

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When R ¹ , R ² and R ³ are a haloalkyl group and have an aryl group as a substituent, R ¹ , R ² and R ³ are an aralkyl group when they have a halogen atom as a substituent.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. Specific examples thereof include a phenyl group, an? -Methylphenyl group, and a naphthyl group.

The aralkyl group is preferably an aralkyl group having 7 to 32 carbon atoms and more preferably an aralkyl group having 7 to 20 carbon atoms. Specifically, benzyl group,? -Methylbenzyl group, phenethyl group, naphthylmethyl group and the like can be exemplified.

The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.

When the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent. When the alkyl group is a straight chain or branched chain alkyl group, the cycloalkyl group may have a carbon And may have a cycloalkyl group having 3 to 12 atoms.

These substituents may be further substituted by the above substituents.

In the formula (a1-1), when R ¹ , R ² and R ³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and as the substituent, an alkyl group having 1 to 6 carbon atoms is preferably exemplified. Examples of the aryl group include a phenyl group, a tolyl group, a silyl group, a cumenyl group, and a 1-naphthyl group.

Further, R ¹ , R ² and R ³ may combine with each other to form a ring together with the carbon atoms to which they are bonded. Examples of the ring structure when R ¹ and R ² , R ¹ and R ³ or R ² and R ³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group , An adamantyl group, and a tetrahydropyranyl group. Among them, a tetrahydrofuranyl group is preferable.

In formula (a1-1), it is preferable that either R ¹ or R ² is a hydrogen atom or a methyl group.

The radically polymerizable monomer which can be used for forming the monomer unit having a moiety represented by the formula (a1-1) may be a commercially available one, or a compound synthesized by a known method may be used. For example, it can be synthesized by reacting (meth) acrylic acid with vinyl ether in the presence of an acid catalyst as shown below.

R ¹¹ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.

R ¹² and R ¹³ are the same as R ² in formula (a1-1) as -CH (R ¹² ) (R ¹³ ), and R ¹⁴ is the same as R ¹ in formula (a1-1) , R ¹⁵ is the same as R ³ in formula (a1-1), and the preferable ranges thereof are also the same.

The above-mentioned synthesis may be carried out by previously copolymerizing (meth) acrylic acid with other monomers and then reacting with vinyl ether in the presence of an acid catalyst.

Specific preferred examples of the monomer unit (a-1-2) having a carboxyl group-protected residue by an acid-decomposable group include the following monomer units. R represents a hydrogen atom or a methyl group.

[Monomer unit (a-1-3) having a residue whose phenolic hydroxyl group is protected with an acid-decomposable group]

- monomer unit having a phenolic hydroxyl group -

Examples of the monomer unit having a phenolic hydroxyl group include a monomer unit in a hydroxystyrene-based monomer unit or a novolak-based resin. Among the monomer units having a phenolic hydroxyl group, the monomer units represented by the formula (a1-2) are preferred from the viewpoints of transparency and sensitivity.

(In the formula (a1-2), R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ represents a single bond or a divalent linking group, R ²² represents a halogen atom or an alkyl group, a represents an integer of 1 to 5 , b represents an integer of 0 to 4, and a + b is not more than 5. When two or more R ²² are present, these R ²² may be the same or different and may be the same)

In formula (a1-2), R ²⁰ represents a hydrogen atom or a methyl group, and is preferably a methyl group.

R ²¹ in the formula (a1-2) represents a single bond or a divalent linking group. In the case of a single bond, it is preferable since the sensitivity can be improved and the transparency of the cured film can be improved. Examples of the divalent linking group of R ²¹ include an alkylene group and specific examples of R ²¹ is an alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, , Pentylene group, isopentylene group, neopentylene group, hexylene group and the like. , It is preferable that R ²¹ is a single bond, a methylene group, or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.

In the formula (a1-2), a represents an integer of 1 to 5, but from the viewpoint of the effects of the present invention and from the standpoint of ease of production, a is preferably 1 or 2, and a 1 is more preferable.

It is preferable that the bonding position of the hydroxyl group in the benzene ring is bonded to the 4-position when the carbon atom bonded to R ²¹ is the reference (1-position).

R ²² in the formula (a1-2) is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples thereof include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert- butyl group, a pentyl group, an isopentyl group and a neopentyl group . Is preferably a chlorine atom, a bromine atom, a methyl group or an ethyl group in view of easiness of production.

B represents 0 or an integer of 1 to 4;

A monomer unit having a phenolic hydroxyl group protected with an acid-decomposable group,

The monomer unit having a residue in which the phenolic hydroxyl group is protected with an acid-decomposable group is a monomer unit having a residue in which the phenolic hydroxyl group of the monomer unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below.

As the acid decomposable group, known ones can be used as described above, and there is no particular limitation. Of the acid-decomposable groups, those in which the phenolic hydroxyl group is protected with an acetal, or a monomer unit having a phenolic hydroxyl group-keto protected residue are particularly preferable from the viewpoints of sensitivity and storage stability of the resin composition. Among the acid decomposable groups, from the viewpoint of sensitivity, it is more preferable that the phenolic hydroxyl group is an acetal or ketal-protected residue represented by the above formula (a1-1). When the phenolic hydroxyl group is an acetal or ketal protected residue represented by the above formula (a1-1), the residue has a structure of -Ar-O-CR ¹ R ² (OR ³ ) as a whole. Ar represents an arylene group.

Preferable examples of the acetal ester structure for protecting the phenolic hydroxyl group include a combination of R ¹ = R ² = R ³ = methyl group, R ¹ = R ² = methyl group and R ³ = benzyl group.

Examples of the radically polymerizable monomer that can be used for forming a monomer unit having a phenolic hydroxyl group having an acetal or ketal protected moiety include a 1-alkoxyalkyl protected product of hydroxystyrene, a tetra A 1-alkoxyalkyl protected form of? -Methylhydroxystyrene, a tetrahydropyranyl protected form of? -Methyl-hydroxystyrene, a 1-alkoxyalkyl protected form of 4-hydroxyphenyl methacrylate , Tetrahydropyranyl protected form of 4-hydroxyphenyl methacrylate, and the like.

As the acetal protecting group and ketal protecting group of the phenolic hydroxyl group, the formula (a1-1) is preferable. These may be used alone or in combination of two or more.

Specific preferred examples of the monomer unit (a-1-3) include the following monomer units, but the present invention is not limited thereto. In the following monomer unit, R represents a hydrogen atom or a methyl group.

Further, it is preferable that the monomer unit (a-1) is a monomer unit having a carboxyl group or a residue in which the phenolic hydroxyl group is protected with a 1-ethoxyethyl group or a tetrahydrofuranyl group.

The content of the monomer unit (a-1) in the component A is preferably from 3 to 70 mol%, more preferably from 10 to 65 mol%, and most preferably from 20 to 20 mol%, based on all monomer units of the component A, To 60 mol% is more preferable.

(a-2) a monomer unit having a crosslinkable group

Component A has at least (a-2) a monomer unit having a crosslinkable group.

The crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction in the heat treatment. Examples of the monomer unit having a preferable crosslinkable group include a monomer unit containing at least one selected from the group consisting of a monomer unit having an epoxy group and / or an oxetanyl group and a monomer unit having an ethylenic unsaturated group. More specifically, the following can be mentioned.

The monomer unit (a-2) is preferably a monomer unit (a-2-1) having an epoxy group and / or oxetanyl group from the viewpoints of storage stability and cured film characteristics.

<Monomer Unit (a-2-1) Having an Epoxy Group and / or an Oxetanyl Group>

The component A preferably has a monomer unit (a-2-1) having an epoxy group and / or an oxetanyl group. Component A may have both a monomer unit having an epoxy group and a monomer unit having an oxetanyl group. From the viewpoint of transparency of the cured product, the component A preferably has a monomer unit having an oxetanyl group.

As the group having an epoxy group, a glycidyl group and a 3,4-epoxycyclohexylmethyl group are preferably exemplified, as long as they have an epoxy ring, though there is no particular limitation.

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

The monomer unit (a-2-1) may have at least one epoxy group or oxetanyl group in one monomer unit, and may contain at least one epoxy group and at least one oxetanyl group, at least two epoxy groups, or two Or more oxetanyl group, and it is preferably, but not limited to, a total of 1 to 3 epoxy groups and / or oxetanyl groups, more preferably 1 or 2 epoxy groups and / or oxetanyl groups in total , An epoxy group or an oxetanyl group.

Specific examples of the radically polymerizable monomer that can be used for forming the monomer unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl alpha -ethyl acrylate, alpha -n-propyl acrylate Glycidyl,? -N-butyl acrylate glycidyl, acrylate-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7 -Epoxyheptyl,? -Ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidylether, the paragraph of Patent No. 4168443 Compounds containing an alicyclic epoxy skeleton described in Nos. 0031 to 0035, and the like.

Examples of the radically polymerizable monomers that can be used for forming the monomer unit having an oxetanyl group include (meth) acrylic esters having an oxetanyl group as described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2001-330953 .

Examples of the radically polymerizable monomer which can be used for forming the monomer unit (a-2-1) are a monomer containing a methacrylic acid ester structure and a monomer containing an acrylic ester structure.

Among these monomers, glycidyl methacrylate, glycidyl acrylate, compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443, and compounds disclosed in JP-A-2001-330953 (Meta) acrylic acid esters having an oxetanyl group as described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-

Particularly preferred from the viewpoint of heat-resistant transparency are monomer units derived from somewhere among acrylic acid (3-ethyloxetan-3-yl) methyl and methacrylic acid (3-ethyloxetan-3-yl) methyl.

These monomer units (a-2-1) may be used alone or in combination of two or more.

Specific preferred examples of the monomer unit (a-2-1) include the following monomer units.

<Monomer unit having an ethylenically unsaturated group (a-2-2)>

As a monomer unit (a-2) having a crosslinkable group, a monomer unit having an ethylenic unsaturated group (a-2-2) can be mentioned.

The monomer unit (a-2-2) having an ethylenically unsaturated group is preferably a monomer unit having an ethylenically unsaturated group in the side chain, a monomer unit having an ethylenic unsaturated group at the end and having a side chain of 3 to 16 carbon atoms And more preferably a monomer unit having a side chain represented by the formula (a2-2-2).

(In the formula (a2-2-2), R ¹ represents a divalent linking group having 1 to 13 carbon atoms, and R ² and R ³ each independently represent a hydrogen atom or a methyl group)

R ¹ may be a divalent linking group having 1 to 13 carbon atoms, but preferably includes an alkenyl group, a cycloalkenyl group, an arylene group, or a group formed by combining these groups, and further preferably an ester bond, an ether bond, an amide bond, Or a combination thereof. The divalent linking group may have a substituent such as a hydroxy group or a carboxy group at an arbitrary position.

The content of the monomer unit (a-2) in the component A is preferably from 5 to 60 mol%, more preferably from 10 to 55 mol%, still more preferably from 20 to 50 mol%, based on the total monomer units of the component A Particularly preferred. By containing the monomer unit (a-2) in the above ratio, the physical properties of the cured film become good.

(a-3) a monomer unit having an alkali-soluble group

The component A preferably has a monomer unit (a-3) having an alkali-soluble group.

The monomer unit (a-3) having an alkali-soluble group has a function of imparting alkali solubility to the component A. As a result, the component A dissolves in an alkali solution (developer) at the time of development, so that the component A containing the monomer unit (a-3) can be easily developed by a developer. Further, the alkali-soluble group-containing monomer can be obtained by crosslinking using a crosslinking agent, or by reaction with an epoxy group or an oxetane group (for example, a group derived from the monomer unit (a-2-1) To give hardness to the obtained cured product.

The alkali-soluble group in the monomer unit (a-3) having an alkali-soluble group may be any group that can be usually used in the field of resists, and examples thereof include a carboxyl group and a phenolic hydroxyl group. Representative examples of the monomer unit (a-3) having an alkali-soluble group include monomer units derived from an unsaturated carboxylic acid or an acid anhydride thereof, hydroxystyrene or a derivative thereof, and the like.

As the monomer unit (a-3), a monomer unit having a carboxyl group or a monomer unit having a phenolic hydroxyl group can be used suitably. Among these, a monomer unit derived from an unsaturated carboxylic acid or an acid anhydride thereof is particularly preferable.

Examples of the unsaturated carboxylic acid or its acid anhydride include an?,? - unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid and an acid anhydride (maleic anhydride, itaconic anhydride, . Of these, acrylic acid and methacrylic acid are particularly preferable. The monomer unit (a-3) having an alkali-soluble group may be used singly or in combination of two or more thereof.

(a-4) a monomer unit having an aromatic ring

The component A is preferably a monomer unit other than the monomer units (a-1) to (a-3) and has a monomer unit (a-4) having an aromatic ring from the viewpoint of refractive index.

Examples of the monomer forming the monomer unit (a-4) include styrenes and (meth) acrylic acid esters having an aromatic ring.

Of these, monomer units derived from styrene are preferable.

(a-5) Other monomer units

The component A may have monomer units (a-5) other than the monomer units (a-1) to (a-4) within the range that does not impair the effect of the present invention.

Examples of the radically polymerizable monomer that can be used to form the monomer unit (a-5) include the compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623 (provided that the monomer units (a-1) to (a-4).

Further, the compounds described below and the like are also exemplified.

Examples of the polyoxyalkylene chain-containing (meth) acrylate monomer include ethylene oxide-modified cresol acrylate (Aronix TO-901), ethylene oxide modified dodecyl acrylate (Aronix TO-950) Ethylhexyl polyethylene glycol acrylate (trade name: Aronix TO-946), 2-ethylhexyl polyethylene glycol acrylate (trade name: ARONIX TO- 947), 2-ethylhexylpolyethylene glycol acrylate (Aronix TO-948), 2-ethylhexyl polyethylene glycol acrylate (Aronix TO-949), manufactured by Soko Dojo Kosei;

(Trade name: LIGHT ACRYLATE EC-A), methoxy-triethylene glycol acrylate (trade name: light acrylate MTG-A), methoxy-polyethylene glycol acrylate (Trade name: LIGHT ACRYLATE NP-4EA), nonylphenyl-polyoxyethylene (trade name: LIGHT ACRYLATE P-200A), nonylphenyl-polyoxyethylene chain adduct acrylate Chain adduct acrylate (trade name: LIGHT ACRYLATE NP-8EA), manufactured by Ishigakagaku Corporation;

(Trade name: Blemmer PE-200), polyethylene glycol methacrylate (trade name: Blemmer PE-90), polyethylene glycol methacrylate (trade name: Blemmer AE-350), polyethylene glycol methacrylate (Trade name: Blemmer PE-350), methoxypolyethylene glycol monoacrylate (trade name: Blemmer AME-400), methoxypolyethylene glycol methacrylate (trade name: Blemmer PME-100), methoxypolyethylene glycol methacrylate (Trade name: Blemmer PME-200), methoxypolyethylene glycol methacrylate (trade name: Blemmer PME-400), polypropylene glycol methacrylate (trade name: Blemmer PP-500), polypropylene glycol methacrylate (Blemmer PP-800), polyethylene glycol polypropylene glycol methacrylate (Blemmer 70PEP-370B), polyethylene glycol polytetramethylene glycol methacrylate (trade name: : Blemmer 50PET-800), octoxypolyethylene glycol polypropylene glycol monomethacrylate (Blemmer 50POEP-800B), octoxypolyethylene glycol polyoxypropylene glycol monomethacrylate (trade name: Blemmer 50AOEP-800B) , Manufactured by Nippon Oil &amp;

(Trade name: NK Ester M-90G), methoxyethyleneglycol methacrylate (trade name: NK Ester M-20G), methoxydiethylene glycol methacrylate (trade name: NK Ester M- , Phenoxyethylene glycol acrylate (trade name: NK ester AMP-20G), and Shin-Nakamura Kagaku Kogyo Co., Ltd., and the like.

Of these, 2-hydroxyethyl (meth) acrylate and dicyclopentanyl (meth) acrylate are preferable. The component A may have one monomer unit (a-5) alone or two or more different monomer units (a-5).

The content of the monomer unit (a-5) in the component A is preferably 0 to 40 mol% based on the total monomer units of the component A.

When the component A contains the monomer unit (a-5), the content of the monomer unit (a5) in the component A is preferably from 1 to 40 mol% based on the total monomer units of the component A, , More preferably from 5 to 30 mol%, and particularly preferably from 5 to 25 mol%.

The method of introducing each monomer unit of the component A may be either a polymerization method or a polymer reaction method, and these two methods may be used in combination. The component A may be used alone or in combination of two or more kinds in the resin composition.

The content of the component A in the resin composition of the present invention is preferably 20 to 99% by weight, more preferably 40 to 97% by weight, and more preferably 60 to 95% by weight, based on the total solid content of the resin composition More preferable. When the content is within this range, pattern formation property upon development can be improved, and a cured product having a higher refractive index can be obtained. The solid content of the resin composition means an amount excluding volatile components such as a solvent.

In the resin composition of the present invention, a resin other than the component A may be used in combination within the range not impairing the effect of the present invention. However, the content of the resin other than the component A is preferably smaller than the content of the component A.

(Component B) particles

The resin composition of the present invention includes particles for the purpose of controlling the refractive index.

The particles preferably have a higher refractive index than the refractive index of the resin composition made of a material excluding the particles. More specifically, particles having a refractive index of 1.50 or more in light having a wavelength of 400 to 750 nm are more preferable, More preferably 1.70 or more, and particularly preferably 1.90 or more.

Here, the refractive index in the light having a wavelength of 400 to 750 nm is 1.50 or more, which means that the average refractive index in the light having the wavelength in the above range is 1.50 or more. Refractive index of 1.50 or more is not required. The average refractive index is a value obtained by dividing the sum of measured values of the refractive index for each light having the wavelength in the above range by the number of measurement points.

Examples of the particles having such a high refractive index include inorganic particles such as inorganic oxide particles, organic particles, and hybrid particles of an organic material and an inorganic material. Among them, inorganic oxide particles are preferable because of high transparency and light transmittance.

As the inorganic oxide particles having high light transmittance and high refractive index, particles of Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Oxide particles containing atoms such as Zn, B, Al, Si, Ge, Sn, Pb, Bi and Te are preferable and titanium oxide, zinc oxide, zirconium oxide, indium / tin oxide and antimony / And titanium oxide is particularly preferable. As the titanium oxide, a rutile type having a high refractive index is particularly preferable. These inorganic particles may be treated with an organic material to impart dispersion stability.

In order not to lower the transparency of the resin composition, the primary particle size of these particles is preferably from 1 to 350 nm, particularly preferably from 3 to 100 nm. Here, the primary particle size of the particles refers to the arithmetic mean of 200 particle diameters of arbitrary particles measured by an electron microscope. When the shape of the particle is not spherical, the longest side is a diameter.

In the resin composition of the present invention, the content of the particles having the refractive index of 1.50 or more in the light having the wavelength in the above-mentioned range is preferably determined in consideration of the refractive index, light transmittance and the like required for the optical member obtained by the resin composition However, it is preferably 5 to 80% by weight, more preferably 20 to 70% by weight, based on the total solid content of the resin composition.

In the present invention, the particles may be provided for use as a dispersion prepared by mixing and dispersing a suitable dispersant and a solvent in a mixing device such as a ball mill or a rod mill.

Examples of the solvent used in the preparation of the dispersion include, in addition to the solvent (Component C) described below, 1-propanol, 2-propanol, 1-butanol, 2- Alcohols such as pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, neopentanol, cyclopentanol, 1-hexanol and cyclohexanol .

As the dispersing agent, those described in the following (component G) dispersing agent can be preferably exemplified.

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

(Component C) Solvent

The resin composition of the present invention contains (Component C) a solvent.

It is preferable that the resin composition of the present invention is prepared as a solution in which the component A and the component B and any other components of the various additives described below are dissolved or dispersed in the (Component C) solvent.

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

Of these solvents, diethylene glycol ethyl methyl ether and / or propylene glycol monomethyl ether acetate are preferable, and propylene glycol monomethyl ether acetate is particularly preferable.

The solvent which can be used in the present invention may be used singly or in combination.

The content of the (component C) solvent in the resin composition of the present invention is preferably 50 to 3,000 parts by weight, more preferably 100 to 2,000 parts by weight, and most preferably 150 to 1,500 parts by weight per 100 parts by weight of the content of the component A More preferable.

(Component D) Photoacid generator

When the resin composition of the present invention is used as a photosensitive resin composition, the resin composition of the present invention preferably contains (Component D) a photoacid generator.

As the component D, a compound which responds to an actinic ray having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm and generates an acid is preferable, but it is not limited to the chemical structure. In the case of a photoacid generator which does not directly react with an actinic ray having a wavelength of 300 nm or more, it is preferably used in combination with a sensitizer in combination with a sensitizer so long as it is sensitive to an actinic ray having a wavelength of 300 nm or more and generates an acid Can be used.

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

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

Specific examples thereof include the following.

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

As the diaryliodonium salts, diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethane sulfonate, 4-methoxyphenylphenyliodonium trifluoromethane sulfonate, 4-methoxyphenylphenyliodonium (2'-hydroxy-1'-tetradecarboxy) phenyl iodonium trifluoromethanesulfonate, phenyl 4- (2'-hydroxy-1'- Iodonium hexafluoroantimonate, or phenyl-4- (2'-hydroxy-1'-tetradecarboxy) phenyliodonium p-toluenesulfonate.

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

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

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

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

The resin composition of the present invention preferably contains, as the component D, an oxime sulfonate compound having at least one oxime sulfonate moiety represented by the following formula (1) from the viewpoint of sensitivity. The broken line indicates the bonding position with other chemical structures.

The oxime sulfonate compound having at least one of the oxime sulfonate moieties represented by the above formula (1) is preferably a compound represented by the following formula (2).

^{R 1A -C (R 2A) =} NO-SO 2 -R 3A (2)

In formula (2), R ^1A represents an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, An alkoxy group having 1 to 4 carbon atoms or a cyano group. When R ^1A is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups may be the same or different from the group consisting of a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, And may be substituted by a selected substituent.

In formula (2), R ^2A represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, A phenylene group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl, dialkylamino, morpholino or cyano group which may be substituted with W, R ^2A and R ^1A may be bonded to each other to form a 5-membered ring or a 6-membered ring, and the 5-membered ring or 6-membered ring may be bonded to a benzene ring which may have 1 or 2 arbitrary substituents.

In formula (2), R ^3A represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, A phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms Lt; / RTI &gt;

The alkyl group having 1 to 6 carbon atoms represented by R ^{1A may} be a linear or branched alkyl group and includes, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec- An n-pentyl group, an isoamyl group, an n-hexyl group, or a 2-ethylbutyl group.

Examples of the halogenated alkyl group having 1 to 4 carbon atoms represented by R ^1A include a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, and a 2-bromopropyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ^1A include methoxy group and ethoxy group.

When R ^{1 A} represents a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups may be substituted with a halogen atom (e.g., a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, Butyl group, a tert-butyl group), an alkoxy group having 1 to 4 carbon atoms (for example, a methoxy group, an isopropoxy group, an isopropoxy group, Ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group) and nitro group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ^2A include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i- an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, a n-decyl group and the like.

Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^2A include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, A n-decyloxy group, and the like.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ^2A include a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoro-n-butyl group, - Amyl group.

Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ^2A include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group, Perfluoro-n-amyloxy group, and the like.

Specific examples of the phenyl group which may be substituted with W represented by R ^2A include o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m- Propyl) phenyl group, p- (n-butyl) phenyl group, p- (i- butyl) phenyl group, (o-amyl) phenyl group, o- methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, (n-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (T-amyloxy) phenyl group, p- (i-amyloxy) phenyl group, p- (t-butoxy) phenyl group, Phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4-difluorophenyl group, Dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6- A trifluorophenyl group, a pentachlorophenyl group, a pentabromophenyl group, a pentafluorophenyl group, and a p-biphenylyl group.

Specific examples of the naphthyl group which may be substituted with W represented by R ^2A include a 2-methyl-1-naphthyl group, a 3-methyl-1-naphthyl group, Methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl Methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group and 8-methyl-2-naphthyl group.

Specific examples of the anthranyl group optionally substituted by W represented by R ^2A include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl- Methyl-1-anthranyl, 7-methyl-1-anthranyl, 8-methyl-1-anthranyl, Anthranyl group, 6-methyl-2-anthranyl group, 7-methyl-2-anthranyl group, , 8-methyl-2-anthranyl group, 9-methyl-2-anthranyl group and 10-methyl-2-anthranyl group.

^Examples of the dialkylamino group represented by R ^2A include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, and a diphenylamino group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ^3A include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i- an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, a n-decyl group and the like.

Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^3A include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, A n-decyloxy group, and the like.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ^3A include a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, a perfluoro-n-butyl group, a perfluoro-n - Amyl group.

Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ^3A include a trifluoromethoxy group, a pentafluoroethoxy group, a perfluoro-n-propoxy group, a perfluoro-n-butoxy group, Perfluoro-n-amyloxy group, and the like.

Specific examples of the phenyl group which may be substituted with W represented by R ^3A include an o-tolyl group, an m-tolyl group, a p-tolyl group, an o-ethylphenyl group, a m-ethylphenyl group, Propyl) phenyl group, p- (n-butyl) phenyl group, p- (i- butyl) phenyl group, (o-amyl) phenyl group, o- methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, (n-butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (T-amyloxy) phenyl group, p- (i-amyloxy) phenyl group, p- (t-butoxy) phenyl group, Phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4-difluorophenyl group, Dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6- A trifluorophenyl group, a pentachlorophenyl group, a pentabromophenyl group, a pentafluorophenyl group, and a p-biphenylyl group.

Specific examples of the naphthyl group which may be substituted with W represented by R ^3A include a 2-methyl-1-naphthyl group, a 3-methyl-1-naphthyl group, a 4-methyl- Methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl Methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group and 8-methyl-2-naphthyl group.

Specific examples of the anthranyl group optionally substituted by W represented by R ^3A include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl- Methyl-1-anthranyl, 7-methyl-1-anthranyl, 8-methyl-1-anthranyl, Anthranyl group, 6-methyl-2-anthranyl group, 7-methyl-2-anthranyl group, , 8-methyl-2-anthranyl group, 9-methyl-2-anthranyl group and 10-methyl-2-anthranyl group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by W, the alkoxy group having 1 to 10 carbon atoms, the halogenated alkyl group having 1 to 5 carbon atoms, and the alkoxy halide having 1 to 5 carbon atoms include R ^2A or Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ^3A , the alkoxy group having 1 to 10 carbon atoms, the halogenated alkyl group having 1 to 5 carbon atoms, and the halogenated alkoxy group having 1 to 5 carbon atoms The same can be said.

R ^2A and R ^1A may combine with each other to form a 5-membered or 6-membered ring.

When R ^2A and R ^1A are bonded to each other to form a 5-membered ring or a 6-membered ring, examples of the 5-membered ring or 6-membered ring include a carbocyclic group and a heterocyclic ring. Examples thereof include cyclopentane, cyclohexane, For example, heptane, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyran, pyridine, pyrazine, morpholine, piperidine or piperazine ring. The 5-membered or 6-membered ring may be bonded to a benzene ring which may have an arbitrary substituent. Examples thereof include tetrahydronaphthalene, dihydroanthracene, indene, chromane, fluorene, xanthene or thioxanthene ring systems. . The 5-membered or 6-membered ring may contain a carbonyl group, and examples thereof include cyclohexadieneone, naphthalenone and anthrone ring systems.

One of the favorable aspects of the compound represented by the formula (2) is a compound represented by the following formula (2-1). The compound represented by the formula (2-1) is a compound in which R ^2A and R ^1A in the formula (2) combine to form a 5-membered ring.

(In formula (2-1) of, R ^3A is, and R ^3A and consent of the formula (2), X is an alkyl group, an alkoxy group or a halogen atom, t is an integer of 0 to 3, when t is 2 or 3, plural Xs may be the same or different)

As the alkyl group represented by X, a linear or branched alkyl group having 1 to 4 carbon atoms is preferable. As the alkoxy group represented by X, a straight chain or branched chain alkoxy group having 1 to 4 carbon atoms is preferable. The halogen atom represented by X is preferably a chlorine atom or a fluorine atom.

As t, 0 or 1 is preferable. In the formula (2-1), t is 1, X is a methyl group, the substitution position of X is about ortho, R ^3A is a straight-chain alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- A norbornylmethyl group, or a p-toluyl group is particularly preferable.

Specific examples of the oxime sulfonate compound represented by the formula (2-1) include the following compounds (i), (ii), (iii) and (iv) They may be used alone or in combination of two or more. The compounds (i) to (iv) are commercially available.

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

As a preferred embodiment of the compound represented by the formula (2)

R ^1A represents an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a phenyl group, a chlorophenyl group, a dichlorophenyl group, a methoxyphenyl group, a 4-biphenyl group, a naphthyl group or an anthranyl group;

R ^2A represents cyano group;

R ^3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, An alkoxy group, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

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

In formula (2-2), R ^4A represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a nitro group, and L represents an integer of 0 to 5. R ^3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, A halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

Examples of R ^3A in the formula (2-2) include a methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, , A perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a p- .

As the halogen atom represented by R ^4A , a fluorine atom, a chlorine atom or a bromine atom is preferable.

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

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

L is preferably 0 to 2, and particularly preferably 0 to 1.

Among the compounds represented by the formula (2), preferable examples of the compound included in the compound represented by the formula (2-2) include a compound wherein R ^1A represents a phenyl group or a 4-methoxyphenyl group, R ^2A is a cyano group, and R ^3A is a methyl group, an ethyl group, a n-propyl group, an n-butyl group or a 4-tolyl group.

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

(In formula (1-2) of, R ¹ is an alkyl group, an aryl group or a heteroaryl group, R ² are, each independently, a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ⁶ are, each independently, a halogen An alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, and m represents an integer of 0 to 6)

In the resin composition of the present invention, the (Component D) photoacid generator is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the content of the component A.

(Component E) Heat crosslinking agent

The resin composition of the present invention preferably contains (Component E) a heat crosslinking agent. (Component E) By adding a heat crosslinking agent, a hardened cured film can be obtained. Component E in the present invention is a component other than component A. It is preferable that the component E is other than the (F) alkali-insoluble resin described later.

As the thermal cross-linking agent, a block isocyanate-based cross-linking agent, an alkoxymethyl group-containing cross-linking agent, a (meth) acrylic resin having an epoxy group or a carboxyl group having an epoxy group, and the like can be preferably exemplified. Among them, an epoxy resin having an epoxy group is particularly preferable.

The amount of the component E to be added is preferably 0.05 to 50 parts by weight, more preferably 0.5 to 10 parts by weight, and still more preferably 0.5 to 5 parts by weight based on 100 parts by weight of the content of the component A. [

(Component F) The alkali-insoluble resin

The resin composition of the present invention preferably contains (Component F) an alkali-insoluble resin.

Component F is an alkali-insoluble resin according to the following definition and is also a compound other than component A. As the component F, a resin which does not cause problems such as cloudiness, surface roughness and precipitation due to phase separation with other components when added to the resin composition of the present invention can be used.

In the present invention, the term &quot; alkali insoluble &quot; in the component F means that the solution of the compound (resin) is applied on a substrate and heated at 90 DEG C for 2 minutes to form a coating film (thickness 4 탆) in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 캜 is less than 0.01 탆 / second.

Examples of the component F include an epoxy resin, an acrylic resin, a styrene resin, a polyester resin, a polyacrylonitrile resin, a polycarbonate resin, a polyamide resin, a polyurethane resin, a parahydroxystyrene resin, .

The alkali-insoluble resin (component F) having thermal crosslinkability such as an epoxy resin can also be used as the component (E) thermal crosslinking agent. However, the content of the alkali-insoluble resin having the thermoplasticity (component F) is determined not to be the component E but to the component F treatment.

Further, since the resin composition of the present invention finally obtains a cured film by heat treatment, it is preferable that the component F has a functional group which can be cured by heating, that is, (Component E) also functions as a heat crosslinking agent. The curing by heating may be cured by the component F alone or may be crosslinked by reacting with the epoxy group and / or oxetanyl group in the component A. When the carboxyl group or the phenolic hydroxyl group of the component A has a residue protected by an acid-decomposable group, the carboxyl group or the phenolic hydroxyl group may be reacted and crosslinked.

Examples of such a compound include an epoxy resin, an acrylic resin having an epoxy group and / or an oxetanyl group.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, alicyclic structure containing epoxy resin, Resins and the like.

Examples of the bisphenol A type epoxy resin include epoxy resins such as JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (manufactured by Mitsubishi Kagaku K.K.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 JER 807, JER 4004, JER 4005, JER 4007, JER 4010 (C), EPICLON 830, EPICLON 835 (manufactured by DIC Corporation), LCE-21, RE- EPICLON N-740, EPICLON N-740 (trade name, manufactured by Mitsubishi Kagaku K.K.), and the like, 660, EPICLON N-665, EPICLON N-670, EPICLON N-673 (manufactured by DIC Corporation), and the like, , EPICLON N-680, EPICLON N-690, EPICLON N-695 (manufactured by DIC Corporation) and EOCN-1020 (manufactured by Nihon Kayaku Co., Ltd.) -4000, YX-4000H, YL6121H, YL-6640, YL-6677, YX-7399 EPICLON HP-4032D, and EPICLON HP-4700 (manufactured by DIC Corporation), and the like, as the naphthalene type epoxy resin, EPICLON HP- Examples of the aliphatic epoxy resin include ADEKA RESIN EP-4080S, EP-4085S and EP-4088S (above, ( (Manufactured by ADEKA), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE 3150, EPOLEAD PB 3600 and PB 4700 (manufactured by Daicel Chemical Industries, Ltd.).

In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, EPPN- -502 (manufactured by ADEKA Corporation) and JER1031S (manufactured by Mitsubishi Chemical Corporation).

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

As the acrylic resin, polymers and copolymers of monomers of (meth) acrylic acid esters can be used. Examples of such a monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- (Meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (Meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (Meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, and the like. These monomers may be used singly or in combination.

In the range where the above-mentioned alkali insolubility can be maintained, a polymer obtained by copolymerizing a monomer having a repeating unit of a carboxyl group, a hydroxyl group, an ethylene oxide, and a repeating unit of propylene oxide with a small amount of a monomer of the (meth) Can be used. Examples of such monomers include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid,? -Carboxypolycaprolactone monoacrylate, Caprolactone monomethacrylate, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4- carboxystyrene, 2- (Meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono (Meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, And the like Relate, dipropylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate.

A polymer obtained by copolymerizing a polymer of the (meth) acrylate ester or a monomer having a repeating unit of propylene oxide with a small amount of a carboxyl group, a hydroxyl group, an ethylene oxide repeating unit and a monomer having a crosslinkable group such as an epoxy group or an oxetanyl group Polymers obtained by copolymerizing monomers can be preferably used. Examples of such monomers include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate, glycidyl? -N-butyl acrylate, Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl,? -Ethylacrylic acid-6,7-epoxyheptyl, Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, compounds containing an alicyclic epoxy skeleton described in paragraphs 0031 to 0035 of Japanese Patent No. 4168443, and the like.

Examples of the radically polymerizable monomers that can be used for forming the monomer unit having an oxetanyl group include (meth) acrylic esters having an oxetanyl group as described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2001-330953 .

Among these monomers, glycidyl methacrylate, glycidyl acrylate, compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443, and compounds disclosed in JP-A-2001-330953 (Meta) acrylic acid esters having an oxetanyl group as described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-

Particularly preferred from the viewpoint of heat-resistant transparency are monomer units derived from somewhere among acrylic acid (3-ethyloxetan-3-yl) methyl and methacrylic acid (3-ethyloxetan-3-yl) methyl. These monomer units may be used singly or in combination of two or more.

The amount of the component F to be added is preferably 3 to 40 parts by weight, more preferably 5 to 35 parts by weight, and even more preferably 8 to 30 parts by weight based on 100 parts by weight of the total solid content of the resin composition.

(Component G) Dispersant

The resin composition of the present invention preferably contains (Component G) a dispersant.

As the dispersant, any dispersing system can be used as long as it can improve the dispersibility of the (Component B) particles.

Examples of such commercial dispersants include Dispersive 101, Dispersive 102, Dispersive 103, Dispersive 108, Dispersive 109, Dispersive 100, Dispersive 111, Dispersive 112, Dispersive 116, Dispersive 130, Dispersive 140, Dispersive 142, Dispersive 145, Dispersive 161, Dispersive 162, Dispersive 163, Dispersive 164, Dispersive 166, Dispersive 167, Dispersive 168, Dispersive 170, Dispersive 174, Dispersive 180, Dispervic 183, Dispervik 185, Dispervik 190, Dispervik 191, Dispervik 193, Dispervik 194, Dispervik 198, Dispervik 2000, Dispervik 2001, Dispervik 2008, Dispervik 2009, Dispervik 2010, Dispersive 2014, Dispersive 2015, Dispersive 2022, Dispersive 2025, Dispersive 2050, Dispersive 2070, Dispersive 2096, Dispersive 2150, Dispersive 2155, Dispersive 2163, Dispersive 2164, Dispersive- EFKA 4010, EFKA 4010, EFKA 4020, EFKA 4046, EFKA 4010, EFKA 4010, EFKA 4010, , EFKA 4047, EFKA 4050, EFKA 4055, EFKA 4060, EFKA 4080, EFKA 4400, EFKA 4401, EFKA 4402, EFKA 4403, EFKA 4406, EFKA 4408, EFKA 4300, EFKA 4330, EFKA 4340, EFKA 4015, EFKA 4800, EFKA 5010, EFKA 5065, EFKA 5066, EFKA 5070, EFKA 7500, EFKA 7554 (all manufactured by Chiba Specialty); Sol Spurs 3000, Sol Spurs 9000, Sol Spurs 13000, Sol Spurs 16000, Sol Spurs 17000, Sol Spurs 18000, Sol Spurs 20000, Sol Spurs 21000, Sol Spurs 26000, Sol Spurs 27000, Sol Spurs 28000, Sol Spurs Sol Spurs 32500, Sol Spurs 32550, Sol Spurs 33500, Sol Spurs 35100, Sol Spurs 35200, Sol Spurs 36000, Sol Spurs 36600, Sol Spurs 38500, Sol Spurs 41000, Sol Spurs 41090, Sol Spurs 20000, Sol Spurs D540 Or more, manufactured by Lubrizol Corporation); Agisper PA111, Agisper PB711, Agisper PB821, Agisper PB822, Agisper PB824 (manufactured by Ajinomoto Fine Techno Co., Ltd.); Disperon DA-375, Disperon DA-705, Disperon DA-325, Disperon DA-325, Disperon DA- 725, Disperon PW-36 (manufactured by Kusumoto Chemical Co., Ltd.); And fluorene DOPA-14, fluorene DOPA-15B, fluorene DOPA-17, fluorene DOPA-22, fluorene DOPA-44, fluorene TG-710, , And ANTI-TERRA-205 (manufactured by BICKEMI Co., Ltd.).

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

Particularly, in the present invention, it is preferable to use a dispersant having a predetermined acid value (hereinafter also referred to as &quot; acid dispersant &quot;) as a dispersant. The acidic dispersant has good adsorptivity to the inorganic particles, and as a result, good dispersibility can be obtained and the pigment dispersion can be made to have a low viscosity. Specific examples of the acidic dispersant include Dispersive P104, Dispersive P104S, Dispersive 220S, Dispersive 110, Dispersive 111, Dispersive 170, Dispersive 171, Dispersive 174 and Dispersive 2095 (manufactured by Big Chemie); EFKA 5010, EFKA 5065, EFKA 5066, EFKA 5070, EFKA 7500, EFKA 7554 (all manufactured by Chiba Specialty); Sol Spurs 3000, Sol Spurs 16000, Sol Spurs 17000, Sol Spurs 18000, Sol Spurs 36000, Sol Spurs 36600 and Sol Spurs 41000 (manufactured by Lubrizol Corporation).

The content of the dispersant in the resin composition of the present invention is preferably from 50 to 3,000 parts by weight, more preferably from 100 to 2,000 parts by weight, and further preferably from 150 to 1,500 parts by weight, per 100 parts by weight of the component B content.

<Other components>

The resin composition of the present invention may contain other components other than the above-mentioned components A to G.

As other components, it is preferable to add a sensitizer (component H) or a development accelerator (component I) from the viewpoint of sensitivity.

The resin composition of the present invention preferably contains an adhesion improver (component J) from the viewpoint of substrate adhesion, and preferably contains a basic compound (component K) from the viewpoint of liquid storage stability, (Component L), a surfactant (a fluorine-based surfactant, a silicone-based surfactant, etc.).

If necessary, the resin composition of the present invention may further contain an antioxidant, (component N) plasticizer, (component O) thermal radical generator, (component P) thermal acid generator, (component Q) , An ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor.

Hereinafter, other components that the resin composition of the present invention can include will be described.

(Component H) sensitizer

In the resin composition of the present invention, a sensitizer (Component H) may be added in combination with the aforementioned (Component D) photoacid generator in order to accelerate the decomposition thereof.

The sensitizer absorbs the actinic ray or radiation and becomes excited. The sensitizer brought into the excited state comes into contact with the photoacid generator to generate an effect such as electron movement, energy transfer, heat generation and the like. As a result, the photoacid generator decomposes by causing a chemical change to generate an acid.

Examples of preferred sensitizers include compounds having an absorption wavelength in the range of 350 nm to 450 nm belonging to the following compounds.

Polycyclic aromatic compounds (e.g., pyrene, perylene, triphenylene, anthracene), xanthines (for example, fluorescein, eosin, erythrosine, rhodamine B and rose bengal), xanthones , Xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (e.g., thiacarbocyanine, oxacarbocyanine), melothiocyanates (e. (E.g., thiophene, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, Acrolein), acridine (for example, acridone, 10-butyl-2-chloroacridone), anthraquinones (for example, anthraquinone), squarylium Alumium), styryls, basestyryls, coumarins (for example, 7-diethylamino-4-methylcoumarin). Among these sensitizers, anthracene, acridone, coumarin and base styryl are particularly preferable.

The sensitizer may be a commercially available one or may be synthesized by a known synthesis method.

The addition amount of the sensitizer is preferably from 20 to 300 parts by weight, particularly preferably from 30 to 200 parts by weight, per 100 parts by weight of the (D) photoacid generator from the viewpoints of both sensitivity and transparency.

(Component I)

The resin composition of the present invention preferably contains (component I) a development accelerator.

(Component I) As the development accelerator, any compound having a phenomenon of promoting development can be used, but it is preferably a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group, A compound having a carboxyl group or a phenolic hydroxyl group is more preferable. A compound having a carboxyl group or a phenolic hydroxyl group protected by an acid-dissociable group is also particularly preferable.

The molecular weight of the component (I) is preferably 100 to 2,000, more preferably 150 to 1,500, and particularly preferably 150 to 1,000.

As examples of the development accelerator, those having an alkyleneoxy group include polyethylene glycol, methyl ether of polyethylene glycol, and compounds described in JP-A No. 9-222724.

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

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

(Component I) One type of the phenomenon promoting agent may be used alone, or two or more types may be used in combination.

In the resin composition of the present invention, the addition amount of (component I) the phenomenon promoter is preferably from 0.1 to 30 parts by weight, more preferably from 0.2 to 20 parts by weight per 100 parts by weight of the content of the component A from the viewpoints of sensitivity and residual film ratio And most preferably 0.5 to 10 parts by weight.

(Component J) Adhesion improving agent

The resin composition of the present invention preferably contains (Component J) an adhesion improver.

The adhesion improver (component J) that can be used in the resin composition of the present invention is a compound that improves the adhesiveness of an inorganic substance to be a substrate such as a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, &Lt; / RTI &gt; Specific examples thereof include silane coupling agents and thiol compounds. The silane coupling agent as the (J) adhesion improver used in the present invention is intended to modify the interface and is not particularly limited, and known ones can be used.

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

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

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

The content of the (J) adhesion improver in the resin composition of the present invention is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the content of the component A. [

(Component K) Basic compound

The resin composition of the present invention preferably contains (Component K) a basic compound.

(Component K) As the basic compound, any of those used as a chemical amplification resistor can be selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

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

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

Examples of heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, Benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8- 4-methyl morpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, pyrrolidine, piperidine, piperazine, morpholine, 1,8-diazabicyclo [5.3.0] -7-undecene and the like.

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

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

The basic compounds usable in the present invention may be used singly or in combination of two or more.

The content of the (basic K) basic compound in the resin composition of the present invention is preferably 0.001 to 1 part by weight, more preferably 0.002 to 0.2 part by weight, per 100 parts by weight of the content of the component A.

(Component L) Surfactants (fluorine surfactants, silicone surfactants, etc.)

The resin composition of the present invention preferably contains (Component L) a surfactant (a fluorine-based surfactant, a silicone-based surfactant, etc.).

As the surfactant, a copolymer (3) containing the constituent unit A and the constituent unit B shown below may be mentioned as a preferable example. The weight average molecular weight (Mw) of the copolymer is preferably 1,000 or more and 10,000 or less, and more preferably 1,500 or more and 5,000 or less. The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC).

In the copolymer (3), R ²¹ and R ²³ each independently represent a hydrogen atom or a methyl group, R ²² represents a straight chain alkylene group having 1 to 4 carbon atoms and R ²⁴ represents a hydrogen atom or a C1- P represents an integer of not less than 10% by weight and not more than 80% by weight, q represents an amount of not more than 20% by weight, and L represents an alkylene group having 3 to 6 carbon atoms, Or more and 90% by weight or less, r is an integer of 1 or more and 18 or less, and n is an integer of 1 or more and 10 or less.

L in the constituent unit B is preferably an alkylene group represented by the following formula (4).

In the formula (4), R ²⁵ represents an alkyl group having 1 to 4 carbon atoms, and from the viewpoint of compatibility and wettability to the surface to be coated, an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl group having 2 or 3 carbon atoms is more preferable Do.

It is also preferable that the sum (p + q) of p and q is p + q = 100, that is, 100% by weight.

Specific examples of the fluorine-based surfactant and the silicon-based surfactant are described in Japanese Patent Application Laid-Open Nos. 62-36663, 61-226746, 61-226745, 62-170950, 63 Surfactants disclosed in the respective publications such as Japanese Patent Application Laid-Open No. 3-24454, Japanese Patent Application Laid-Open Nos. 7-230165, 8-62834, 9-54432, 9-5988, and 2001-330953 And a commercially available surfactant may be used. Examples of commercially available surfactants that can be used include surfactants EF301 and EF303 (manufactured by Mitsubishi Materials Corporation, Mitsubishi Materials Corporation), Fluorad FC430 and 431 (manufactured by Sumitomo 3 Electronics Co., Ltd.) , Megaface F171F780F, F173, F176, F189 and R08 (manufactured by DIC Corporation), Surflon S-382, SC01, 102, 103, 104, 105 and 106 (manufactured by Asahi Glass Co., , A fluorine surfactant such as PolyFox series (manufactured by OMNOVA), or a silicone surfactant. The polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

These surfactants may be used singly or in combination of two or more. Further, a fluorine-based surfactant and a silicon-based surfactant may be used in combination.

The addition amount of the (component L) surfactant (fluoric surfactant, silicone surfactant, etc.) in the resin composition of the present invention is preferably 10 parts by weight or less, more preferably 0.01 to 10 parts by weight More preferably 0.01 to 1 part by weight.

(Component M) Antioxidant

The resin composition of the present invention may contain an antioxidant (component M). (Component M) By adding an antioxidant, coloring of the cured film can be prevented or reduction in film thickness due to decomposition can be reduced.

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

Examples of commercially available products of phenolic antioxidants include Adekustab AO-60, Adekustab AO-80 (manufactured by ADEKA), Irganox 1098 (manufactured by Ciba Japan Co., Ltd.) have.

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

As the additives other than the antioxidant, various ultraviolet absorbers, metal deactivators, and the like described in "New Development of Polymer Additives (Nikkan Kogyo Shinbashi Co., Ltd.") may be added to the resin composition of the present invention.

(Component N) Plasticizer

The resin composition of the present invention may contain (component N) plasticizer.

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

The content of the plasticizer (component N) in the resin composition of the present invention is preferably 0.1 to 30 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the content of the component A. [

(Component O) thermal radical generator

The resin composition of the present invention may contain (component O) a thermal radical generator, and when it contains an ethylenically unsaturated compound such as a compound having an ethylenically unsaturated double bond, the component (O) . As the thermal radical generator, a known thermal radical generator may be used.

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

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

(Component O) One kind of thermal radical generator may be used alone, or two or more kinds thereof may be used in combination.

The content of the heat radical generator (component O) in the resin composition of the present invention is preferably from 0.01 to 50 parts by weight, more preferably from 0.1 to 20 parts by weight, based on 100 parts by weight of the content of the component A, More preferably 0.5 to 10 parts by weight.

(Component P) Thermal acid generator

The resin composition of the present invention may contain (Component P) thermal acid generator.

The thermal acid generator is a compound which generates acid by heat and has a thermal decomposition point of preferably from 130 to 250 캜, more preferably from 150 to 220 캜, for example, by heating, Is a compound which generates a low nucleophilic acid such as carboxylic acid, disulfonylimide and the like.

As the generated acid, preferred is a disulfonylimide substituted with an electron-attracting group such as a sulfonic acid or a substituted alkylcarboxylic acid or an arylcarboxylic acid substituted with an electron-withdrawing group having a pKa of 2 or less, and the like. Examples of the electron-attracting group include a halogen atom such as a fluorine atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.

In the present invention, it is also preferable to use a sulfonic acid ester which does not generate an acid substantially by irradiation with exposure light and generates an acid by heat. The molecular weight of the thermal acid generator is preferably from 230 to 1,000, more preferably from 230 to 800.

The content of the thermal acid generator in the resin composition is preferably 0.5 to 20 parts by weight, particularly preferably 1 to 15 parts by weight, per 100 parts by weight of the content of the component A. [

(Component Q)

For the purpose of improving the sensitivity, the resin composition of the present invention can use (component Q) an acid growth agent. The acid-proliferating agent used in the present invention is a compound capable of generating a further acid by an acid catalytic reaction to increase the concentration of an acid in the reaction system, and is a compound stably present in the absence of acid. Such a compound accelerates the reaction in accordance with the progress of the reaction because one or more acids are elongated in a single reaction. However, since the resulting acid itself undergoes self-decomposition, the strength of the acid generated here is, It is preferable that the integer pKa is 3 or less, particularly 2 or less.

Specific examples of the acid proliferating agent include those described in paragraphs 0203 to 023 of Japanese Patent Application Laid-Open No. 10-1508, paragraphs 0016 to 555 of Japanese Patent Application Laid-Open No. 10-282642, and Japanese Patent Publication No. 9-512498, page 39, line 12 To page 47, page 2, and the like.

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

The content of the acid proliferating agent in the resin composition is preferably from 10 to 1,000 parts by weight based on 100 parts by weight of the (D) photoacid generator from the viewpoint of dissolution contrast between the exposed portion and the unexposed portion, It is more preferable to make the portion.

(Production method of cured product)

The method for producing a cured product of the present invention is not particularly limited as long as it is a method for producing a cured product using the resin composition of the present invention, but it is preferable that the method includes at least steps (a) to (c) in this order. The shape of the cured product obtained by the method for producing a cured product of the present invention is not particularly limited and may be a film-like cured product or any shape, such as a method including the following steps (a) to (c) And may be a cured product in a pattern as described later.

(a) a coating step of applying the resin composition of the present invention on a substrate

(b) a solvent removing step of removing the solvent from the applied resin composition

(c) a heat treatment step of heat-treating the resin composition from which the solvent has been removed

Each step will be described below in order.

<Coating Process (Process (a))>

The method for producing the cured product of the present invention preferably includes (a) a coating step of coating the resin composition of the present invention on a substrate.

In the step (a), it is preferable to form a desired dry film by applying the resin composition of the present invention to a predetermined substrate and removing the solvent by reduced pressure and / or heating (prebaking).

Examples of the substrate material that can be used in the present invention include silicon, silicon dioxide, silicon nitride, alumina, glass, glass-ceramics, gallium arsenide, indium phosphide, copper, aluminum, nickel, iron, Tin oxide coated glass; Organic films such as polyimide and polyester; A metal, a semiconductor, and any substrate containing a patterning region of an insulating material, but are not limited thereto. Optionally, a baking step may be performed on the substrate to remove absorbed moisture prior to application of the resin composition. The coating method on the substrate is not particularly limited, and for example, slit coating method, spraying method, roll coating method, spin coating method, and flexible coating method can be used. In the case of a large substrate, a slit coating method is preferable. Here, a large substrate refers to a substrate having a size of 1 m or more and 5 m or less in each side.

<Solvent removal step (step (b))>

The method for producing the cured product of the present invention preferably includes (b) a solvent removing step for removing the solvent from the applied resin composition.

In the step (b), it is preferable that the solvent is removed from the applied film by reduced pressure (baking) and / or heating to form a dry film on the substrate. The heating conditions are preferably about 70 to 120 DEG C for about 30 to 300 seconds.

The method for producing a resin pattern of the present invention can be suitably used for producing a thick film having a thickness of 4 占 퐉 or more after removal of a solvent since the shape controllability is good. The film thickness after removing the solvent is preferably 4 to 500 mu m, more preferably 4 to 100 mu m.

&Lt; Heat treatment step (step (c)) >

The method for producing a cured product of the present invention preferably includes a heat treatment step (baking step) for heat-treating the resin composition from which the solvent has been removed. The cured film can be formed by heat treatment.

The heat treatment temperature (baking temperature) is preferably 180 to 250 캜, and the heat treatment time is preferably 30 to 150 minutes.

(A-1-1) a monomer unit having a carboxyl group or a phenolic hydroxyl group protected with an acid-decomposable group and (a-2-1) a monomer unit having an epoxy group and / or an oxetanyl group , The acid decomposable group in the monomer unit (a-1-1) is thermally decomposed to produce a carboxyl group or a phenolic hydroxyl group, which is then cross-linked with an epoxy group and / or an oxetanyl group , And a cured film can be formed.

When (Component E) a heat crosslinking agent is used, it is preferable that the (E) thermal crosslinking agent is also thermally crosslinked in the heat treatment step.

(Resin pattern production method)

The method for producing a resin pattern of the present invention is not particularly limited as long as it is a method for producing a resin pattern using the resin composition of the present invention, but it is preferable that the method includes at least steps (1) to (5) in this order.

(1) a coating step of applying the resin composition of the present invention on a substrate

(2) a solvent removing step for removing the solvent from the applied resin composition

(3) an exposure step of exposing the resin composition from which the solvent has been removed to a patterned image by an actinic ray

(4) a developing step of developing the exposed resin composition with an aqueous developing solution

(5) Heat treatment process for heat-treating the developed resin composition

Each step will be described below in order.

<Coating Process (Step (1))>

The resin pattern production method of the present invention preferably includes (1) a coating step of coating the resin composition of the present invention on a substrate.

Step (1) is the same step as step (a), and preferred embodiments are also the same.

<Solvent removal step (step (2))>

The resin pattern production method of the present invention preferably includes a solvent removal step of (2) removing the solvent from the applied resin composition.

The step (2) is the same as the step (b), and the preferred embodiment is also the same.

&Lt; Exposure step (step (3)) >

The resin pattern production method of the present invention preferably includes (3) an exposure step of exposing the resin composition from which the solvent has been removed to a pattern image by an actinic ray.

In the step (3), the substrate provided with the dry coating film is irradiated with an actinic ray of a predetermined pattern. The exposure may be performed through a mask, or a predetermined pattern may be directly drawn.

As the active ray, an active ray having a wavelength of 300 nm or more and 450 nm or less can be preferably used. A low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a laser generator, an LED light source, or the like can be used for exposure by an actinic ray.

When a mercury lamp is used, an actinic ray having a wavelength such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used. The mercury lamp is preferable in that it is suitable for exposure of a large area as compared with a laser.

In the case of using a laser, various lasers can be used without any particular limitation by appropriately selecting a wavelength. For example, as the solid-state (YAG) laser, 343 nm and 355 nm can be used. As the excimer laser, 351 nm (XeF) can be used, and as the semiconductor laser, 375 nm and 405 nm can be used . Of these, 355 nm or 405 nm is more preferable in terms of stability and cost. The laser can be applied to the coating film once or several times.

The laser is preferable to a mercury lamp because it is easy to tighten the focus and a mask for forming a pattern in the exposure process is unnecessary and cost can be reduced.

Examples of the exposure apparatus that can be used in the present invention include, but are not limited to, those available from Callisto (manufactured by V Technology), AEGIS (manufactured by V Technology) and DF2200G (manufactured by Dainippon Screen Co., ) Can be used. Also, devices other than those described above can be used suitably.

If necessary, the irradiation light can be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.

After the exposure process, PEB (post exposure baking process) can be performed before the developing process, if necessary. The temperature for PEB is preferably 30 ° C or higher and 130 ° C or lower, more preferably 40 ° C or higher and 110 ° C or lower, and particularly preferably 50 ° C or higher and 90 ° C or lower.

<Development Process (Step (4))>

The resin pattern manufacturing method of the present invention preferably includes (4) a developing step of developing the exposed resin composition by an aqueous developing solution.

In step (4), development is carried out using an aqueous developer.

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

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

The development time is preferably 30 to 180 seconds, and the developing method may be any of a liquid method, a dipping method, and a shower method. After the development, it is preferable to carry out the water washing for 10 to 90 seconds to form a desired pattern.

The method for producing a resin pattern of the present invention may include a re-exposure step of re-exposing a substrate on which a pattern is formed by an actinic ray between steps (4) and (5) desirable.

The exposure in the re-exposure step may be performed by the same means as the exposure step, but in the re-exposure step, it is preferable to perform the entire exposure on the side where the resin composition film of the substrate is formed.

The preferable exposure amount of the re-exposure step is 100 to 1,000 mJ / cm &lt; 2 &gt;.

<Heat Treatment Process (Step (5))>

The resin pattern production method of the present invention preferably includes a heat treatment step (baking step) for heat-treating the developed resin composition. The cured film can be formed by heat treatment.

The step (5) is the same as the step (c) except that the resin composition from which the solvent has been removed is subjected to the step (4) and the developed resin composition is used.

(Transfer material)

The resin composition of the present invention can be suitably used as a transferring material. Concretely, for example, the resin composition provided on the temporary support can be used as a transfer material to be transferred onto a substrate of a display device or onto a semiconductor substrate.

When the resin composition of the present invention is used as a transfer material to form a resin pattern, the resin pattern production method of the present invention preferably includes the following steps (1 ') to (6') in this order.

(1 ') A coating process of applying the resin composition of the present invention onto a support

(2 ') a solvent removing step of removing the solvent in the applied resin composition

(3 ') Step of transferring the resin composition from which the solvent has been removed to a substrate (permanent support)

(4 ') an exposure process for exposing the transferred resin composition to a patterned image with an actinic ray

(5 ') a developing step of developing the exposed resin composition with an aqueous developing solution

(6 ') Heat treatment process for heat-treating the developed resin composition

<Coating Process (Step (1 '))>

The method for producing a resin pattern of the present invention preferably comprises (1 ') an application step of applying the resin composition of the present invention onto a substrate.

The process (1 ') is the same as the process (a) except that the substrate shown below is used in place of the substrate.

As the branching material, known materials such as polyester and polystyrene can be used. Among them, biaxially stretched polyethylene terephthalate is preferable from the viewpoints of cost, heat resistance and dimensional stability.

The thickness of the branched body is preferably 15 to 200 mu m, more preferably 30 to 150 mu m.

<Solvent removal step (step (2 '))>

The resin pattern manufacturing method of the present invention preferably includes a solvent removing step of removing the solvent in the resin composition (2 ').

The step (2 ') is the same as the step (b), and the preferred embodiment is also the same.

&Lt; Transcription step (step (3 '))

The resin pattern production method of the present invention preferably includes a step of transferring the resin composition from which (3 ') the solvent has been removed to a substrate (permanent support).

The transferring step preferably includes a step of bonding the resin composition from which the solvent has been removed to a substrate (permanent support), and a step of removing the branching agent from the resin composition adhered to the substrate.

The bonding of the resin composition from which the solvent has been removed and the substrate can be carried out by, for example, compression bonding or heat pressing in a heated and / or pressurized roller or flat plate.

Specifically, the laminator and the lamination method described in Japanese Patent Application Laid-Open No. 7-110575, Japanese Patent Application Laid-Open No. 11-77942, Japanese Patent Application Laid-Open No. 2000-334836, and Japanese Patent Laid-Open No. 2002-148794, Low) From the viewpoint of foreign matter, it is preferable to use the method described in Japanese Patent Application Laid-Open No. 7-110575.

The method of removing branch lags is not particularly limited. For example, an adhesive roller having a pressure-sensitive adhesive layer or the like may be brought into contact with a branch support and removed by peeling the branch support from the resin composition which is attached to the substrate. Specifically, the separation of the branches may be carried out by grasping and peeling the end portions of the branches separated from the substrate separated by the continuous separation or the single-wafer separation in which the branches are separated in a continuous winding manner.

The method of peeling the branched body is preferably a method described in Japanese Patent Application Laid-Open No. 2006-297879 for continuous peeling, and a method described in Japanese Patent Application Laid-Open No. 2007-320678 for sheet laminating.

&Lt; Exposure Step (Step (4 ')) &gt;

The resin pattern production method of the present invention preferably includes an exposure step of exposing the resin composition transferred (4 ') to a patterned image by an actinic ray.

The step (4 ') is the same as the step (3), except that the transferred resin composition obtained through the step (3') is used instead of the resin composition from which the solvent has been removed.

&Lt; Development step (step (5 '))

The resin pattern manufacturing method of the present invention preferably includes a developing step of developing the exposed resin composition with an aqueous developing solution (5 ').

Step (5 ') is the same as step (4), and preferred embodiments are also the same.

&Lt; Heat treatment step (step (6 '))

The resin pattern manufacturing method of the present invention preferably includes a heat treatment step of heat-treating the resin composition (6 '). The cured film can be formed by heat treatment.

Step (6 ') is the same as step (5), and preferred embodiments are also the same.

As a method of producing a resin pattern in the case of forming a resin pattern by using the resin composition of the present invention as a transfer material, Japanese Patent Laid-Open No. 2010-72589 can also be referred to.

When the resin composition of the present invention is used as a transfer material and the resin composition of the present invention does not contain a photoacid generator (Component D), the resin pattern production method of the present invention is characterized in that the step (1 ' ), (2 '), (3') and (6 ') in this order.

(Cured product, optical member)

The cured product of the present invention is not particularly limited as long as the resin composition of the present invention is cured, but is preferably a cured product produced by the method of producing a cured product of the present invention or the method of producing a resin pattern.

Further, the cured product of the present invention can be suitably used as an optical member such as a microlens, an optical waveguide, or an antireflection film. The cured product of the present invention can also be suitably used as a member for reducing visibility of a wiring electrode used in a touch panel. In particular, it can be suitably used as a microlens.

[Example]

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

In the following Synthesis Examples, the following abbreviations respectively represent the following compounds.

V-601: Dimethyl-2,2'-azobis (2-methylpropionate)

GMA: glycidyl methacrylate

PGMEA: Propylene glycol monomethyl ether acetate

&Lt; Synthesis of Polymer A1 >

63.2 parts (0.405 molar equivalents) of methacrylic acid tetrahydrofuran-2-yl,

Methacrylic acid (8.2 parts (0.095 molar equivalents)),

69 parts (0.375 molar equivalents) of methacrylic acid (3-ethyloxetan-3-yl) methyl,

2-hydroxyethyl methacrylate (16.3 parts, (0.125 molar equivalents)),

And a mixed solution of propylene glycol monomethyl ether acetate (PGMEA) (120 parts) was heated to 70 占 폚 under a nitrogen stream. Azobis (2-methylpropionate), Wako Pure Chemical Industries, Ltd.) (12.0 parts) and PGMEA (80 parts) were mixed while stirring the mixture solution, Was added dropwise over 3.5 hours. After completion of the dropwise addition, the reaction was carried out at 70 DEG C for 2 hours to obtain a PGMEA solution of the polymer A1. Further, PGMEA was added to adjust the solid concentration to 40% by weight.

The polymer A1 thus obtained had a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 15,000.

<Synthesis of Polymers A2 to A7, A'1, A'2, and B1 to B5>

The synthesis of the polymer A1 was carried out in the same manner as in the synthesis of the polymer A1 except that the respective monomers used in the synthesis of the polymer A1 were changed to the monomers forming the respective monomer units shown in Table 1 and the amounts of the monomers forming the respective monomer units were changed to those shown in Table 1 To thereby synthesize Polymers A2 to A7, A'1, A'2, and B1 to B5, respectively. The addition amount of the radical polymerization initiator V-601 was adjusted so as to have the molecular weights shown in Table 1, respectively.

[Table 1]

The amounts shown in Table 1 are molar ratios and represent the copolymerization ratios of the monomer units derived from the respective monomers described in the column of the type. In Table 1, "-" indicates that the monomer unit is not used.

The abbreviations in Table 1 are as follows.

MAEVE: 1-ethoxyethyl methacrylate

MATHF: tetrahydrofuran-2-yl methacrylate

GMA: glycidyl methacrylate

OXE-30: Methacrylic acid (3-ethyloxetan-3-yl) methyl (Osaka Yuki Kagaku Kogyo Co., Ltd.)

St: Styrene

HEMA: 2-hydroxyethyl methacrylate

MAA: methacrylic acid

MMA: methyl methacrylate

t-BuMA: t-butyl methacrylate

HS-EVE: The following compound (4- (1-ethoxy) ethoxystyrene)

AllylMA: Allyl methacrylate

A: Nonyl phenyl-polyoxyethylene chain adduct acrylate

(Trade name: light acrylate NP-4EA manufactured by Kyoeisha Chemical Co., Ltd.)

B: methoxypolyethylene glycol methacrylate

(Trade name: BLEMMER PME-400 manufactured by Nippon Oil Co., Ltd.)

C: Octoxypolyethylene glycol Polyoxypropylene glycol monomethacrylate (trade name: Blemmer 50AOEP-800B manufactured by Nippon Oil Co., Ltd.)

(Adjustment of dispersion liquid)

The dispersions of the compositions in Table 2 were combined, mixed with 150 parts by weight of zirconia beads (0.3 mm?), And dispersed for 9 hours using a paint shaker. The zirconia beads (0.3 mm?) Were separated by filtration to obtain dispersions Q1 and Q2, respectively.

With respect to the dispersion liquid Q2, the components described in Table 2 were mixed and stirred without performing dispersion.

The average primary particle diameter of the used TTO-51C (manufactured by Ishihara Sangyo Co., Ltd.) was 11 nm and the average primary particle diameter of the nano-used OZ-S30K-AC (manufactured by Nissan Chemical Industries, 18 nm.

[Table 2]

(Adjustment of the Photosensitive Material Liquid)

The components shown in Tables 3 and 4 were mixed to prepare a homogeneous solution, which was then filtered using a polyethylene filter having a pore size of 0.2 mu m to prepare a photosensitive material solution (sensitizing solution).

[Table 3]

[Table 4]

The units of amounts in Tables 3 and 4 are parts by weight.

The abbreviations in Tables 3 and 4 are as follows.

C1: Propylene glycol monomethyl ether acetate

D1: Oxime sulfonate compound synthesized by the following synthesis method

D2:? - (p-toluenesulfonyloxyimino) phenylacetonitrile (synthesis method is as shown below)

D3: CGI1397 (the following compound, manufactured by Chiba Specialty Chemicals)

D4: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate

E1: JER157S65 (manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent: 200 to 220 g / eq)

H1: 9,10-dibutoxyanthracene (DBA)

J1: 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

K1: 1,5-Diazabicyclo [4.3.0] -5-nonene

K2: Triphenylimidazole

L1: Compound W-3 shown below

&Lt; Synthesis method of D1 >

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

Acetic acid (7.3 g) and a 50% hydroxylamine aqueous solution (8.0 g) were added to the suspension of the obtained ketone compound (3.0 g) and methanol (30 ml), and the mixture was heated to reflux. After allowing to cool, water (50 ml) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).

The obtained oxime compound (1.8 g) was dissolved in acetone (20 ml), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, the temperature was raised to room temperature, . Water (50 ml) was added to the reaction solution, and the precipitated crystals were filtered and then slurry was rinsed with methanol (20 ml), filtered and dried to obtain D1 (2.3 g).

In addition, ¹ H-NMR spectrum of D1 (300MHz, CDCl ₃₎ is, δ = 8.3 (d, 1H ), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q,

&Lt; Synthesis method of D2 &

Α- (p-toluenesulfonyloxyimino) phenylacetonitrile was synthesized according to the method described in paragraph 0108 of Japanese Patent Laid-Open No. 2002-528451.

[Table 5]

The numbers on the lower right of the brackets in F4, F5, F'1 and F'2 indicate the molar ratio.

<Evaluation of Alkali Solubility of Component F>

PGMEA solutions were prepared for each of the components F listed in Table 5 below. The dissolution rate of the coating film (thickness 4 占 퐉) of the component F formed by applying each solution onto the substrate and heating at 90 占 폚 for 2 minutes to an aqueous solution of 2.38 wt% tetramethylammonium hydroxide at 23 占 폚 was measured I investigated. "Alkali insoluble" when the dissolution rate was less than 0.01 탆 / second and "alkali solubility" when it was 0.01 탆 / second or more. The results are shown in Table 5.

(Preparation of photosensitive resin composition)

According to Table 6, a photosensitive resin solution (photosensitive solution) and a dispersion were mixed to prepare a homogeneous solution, and then a polyethylene filter having a pore size of 0.2 mu m was used and filtered to prepare photosensitive resin compositions. Each of the obtained photosensitive resin compositions was subjected to the following evaluations. The units of the amounts in Table 6 are parts by weight. However, R11 used in Example 15 is not a photosensitive, but a thermosetting resin composition.

The results are shown in Table 7.

[Table 6]

(1) Evaluation of sensitivity

A photosensitive resin composition was coated on a silicon wafer having a silicon oxide film by a slit and prebaked on a hot plate at 90 캜 for 120 seconds to form a coating film having a thickness of 15 탆.

Next, using an i-line stepper (FPA-3000i5 ⁺ manufactured by Canon Inc.), exposure was carried out through a 20 μm line-and-space mask. Heated on a hot plate at 50 DEG C for 60 seconds, developed with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 DEG C for 60 seconds by the liquid method, and further rinsed with ultrapure water for 45 seconds. The exposure amount (Eopt, optimum exposure amount) when resolving the line-and-space of 20 mu m to 1: 1 by these operations was taken as sensitivity.

1: Eopt is less than 50 mJ / cm 2

2: Eopt less than 50mJ / cm2 and less than 150mJ / cm2

3: Eopt more than 150mJ / ㎠

High sensitivity is preferable, and 1 or 2 is a practical range.

(2) Evaluation of resolution

A photosensitive resin composition was slit-coated on a silicon wafer having a silicon oxide film. Next, the solvent was removed on a hot plate at 90 DEG C for 120 seconds to form a coating film having a thickness of 10 mu m.

Next, an i-line stepper (FPA-3000i5 ⁺ manufactured by Canon Inc.) was used to expose an optimum exposure amount through a 1: 1 line-and-space mask. And heated at 50 캜 for 60 seconds on a hot plate.

Next, the resist film was developed by a liquid method at 23 DEG C for 60 seconds with a 2.38 wt% tetramethylammonium hydroxide aqueous solution, and further rinsed with ultrapure water for 45 seconds. Cm 2 (measured by i-line) using an ultra-high pressure mercury lamp, and then heated in an oven at 140 캜 for 30 minutes and then heated at 220 캜 for 30 minutes to obtain a pattern. This pattern was observed with an optical microscope.

This operation was started from the width of the line and space of the mask of 10 mu m, and the minimum width at which the pattern was clearly formed was defined as the resolution while narrowing the width by 1 mu m.

1: resolution less than 5 탆

2: resolution 5 탆 or more and less than 10 탆

3: Resolution 10 μm or more

(3) Evaluation of shape of pattern

A photosensitive resin composition was slit-coated on a glass substrate. Next, the solvent was removed on a hot plate at 90 DEG C for 120 seconds to form a coating film having a thickness of 20 mu m.

Next, using a mercury lamp exposing machine (MPAsp-H750, manufactured by Canon Inc.), exposure was performed at an optimum exposure amount through a mask having a space width of 40 탆 and a line-and-space 1: 1. And heated at 50 캜 for 60 seconds on a hot plate. Next, the resist film was developed by a liquid method at 23 DEG C for 60 seconds with a 2.38 wt% tetramethylammonium hydroxide aqueous solution, and further rinsed with ultrapure water for 45 seconds.

The shape of the pattern was observed with an electron microscope by heating in an oven at 230 DEG C for 60 minutes.

In addition, it is preferable that the shape of the pattern be a rounded shape by cutting off the angle.

(4) Evaluation of pencil hardness (mechanical strength evaluation)

The resin composition was slit-coated on a glass substrate. Next, the solvent was removed on a hot plate at 90 DEG C for 120 seconds to form a coating film having a thickness of 20 mu m. Cm 2 (measured by i-line) using ultrahigh pressure mercury, and then heated in an oven at 230 캜 for 60 minutes to obtain a cured film of a solid film.

The pencil hardness of the obtained cured film was measured according to JIS K5600-5-4. Stiffness is preferred.

1: 5H or more (hard)

2: 3H to 4H

3: 2H or less (softness)

(5) Evaluation of refractive index

The resin composition of Table 6 was coated on a silicon wafer substrate using a spinner and dried at 80 DEG C for 120 seconds to form a film having a thickness of 0.5 mu m. This substrate was exposed at 300 mJ / cm 2 (measured by i-line) using ultrahigh pressure mercury, and then heated in an oven at 220 ° C for 60 minutes.

The refractive index of the cured film at 589 nm was measured using an ellipsometer VUV-VASE (manufactured by JAE URUMU Co., Ltd.). The measurement results are shown in Table 7. The refractive index is preferably high, more preferably at least 1.7.

&Lt; Evaluation of residual film ratio of unexposed portion &

The photosensitive resin composition of Table 6 was coated on a 100 mm x 100 mm glass substrate (trade name: XG, made by Corning) with a spin coater so as to have a film thickness of 1.0 m and dried (prebaked) for 120 seconds on a hot plate at 90 deg. . Subsequently, this sample was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide at 23 DEG C for 60 seconds by an immersion method, and further rinsed with ultrapure water for 10 seconds. Thereafter, the film thickness was also measured to determine the residual film ratio after development when the original film thickness (1.0 mu m) was taken as 100%. Evaluation criteria are shown below.

1: 90% or more of residual film ratio

2: Residual film ratio is 80% or more and less than 90%

3: residual film ratio less than 80%

The results are shown in Table 7.

It can be seen that the residual film ratio of the unexposed portion is improved by adding the alkali-insoluble component F.

&Lt; Evaluation of solvent resistance &

The photosensitive resin composition of Table 6 was coated on a 100 mm x 100 mm glass substrate (trade name: XG, made by Corning) with a spin coater so as to have a film thickness of 4 μm and dried (prebaked) on a hot plate at 90 ° C for 120 seconds . This substrate was exposed to light at 300 mJ / cm 2 (measured by i-line) using ultrahigh pressure mercury, and then heated in an oven at 220 ° C for 60 minutes.

Subsequently, this substrate was immersed in NMP (N-methylpyrrolidone) solvent at 40 DEG C for 3 minutes, and then rinsed with ultra-pure water for 10 seconds. After that, the film was evaluated for film thickness reduction and film surface appearance. Evaluation criteria are shown below.

1: No film reduction at all

2: slight decrease in film thickness

3: Film reduction is large, surface roughness is also visible

[Table 7]

In Table 7, &quot; x &quot; indicates that evaluation was impossible because the pattern could not be formed. In Table 7, &quot; - &quot; indicates that the resin composition was not evaluated because it is a thermosetting resin composition.

From the evaluation results shown in Table 7, it was found that the sensitivity was higher when the oxime sulfonate compound was used as the photoacid generator.

In addition, when the monomer unit having a residue in which a carboxyl group or a phenolic hydroxyl group is protected with an acid-decomposable group is used as a leaving group, it is found that the sensitivity is higher.

Further, it was found that the obtained cured product was hard as compared with the resin composition containing the particles. Further, it was found that the component A having a crosslinkable group had a hardened product.

Further, from the examples, it was found that the resin composition of the present invention comprising a polymer having a releasing group and particles has a high refractive index. On the other hand, from Comparative Examples 1 and 3, it was found that the refractive index did not improve so much when either of the separator and the particle were absent.

Claims (19)

(Component A) A polymer having (a-1) a monomer unit having an acid and / or a thermal-leaving group and (a-2) a monomer unit having a crosslinkable group,
(Component B) particles,
(Component C) solvent,
Wherein the component B is a metal oxide particle having a refractive index of 1.70 or more in light having a wavelength of 400 to 750 nm. The method according to claim 1,
(Component D) a photoacid generator. The method according to claim 1,
(Component E) A thermosetting agent. The method according to claim 1,
(Component F) An alkali-insoluble resin. 5. The method of claim 4,
Wherein the component F is an alkali-insoluble resin having a crosslinkable group. 6. The method of claim 5,
Component F has an epoxy group as a crosslinkable group. 5. The method of claim 4,
Wherein component F is an epoxy resin or an acrylic resin. The method according to claim 1,
The resin composition according to any one of (a-1) to (a-1), wherein the monomer unit having an acid and / or a thermal desorbing group is a monomer unit having a carboxyl group or a phenolic hydroxyl group protected with an acid-decomposable group. The method according to claim 1,
Wherein the (a-2) monomer unit having a crosslinkable group is (a-2-1) a monomer unit having an epoxy group and / or an oxetanyl group. delete delete The method according to claim 1,
Wherein the metal oxide particles are titanium oxide particles or zirconium oxide particles. The method according to claim 1,
A resin composition, which is a photosensitive resin composition. The method according to claim 1,
Wherein the positive photosensitive resin composition is a positive photosensitive resin composition. The method according to claim 1,
A resin composition for an optical member. Characterized in that it comprises at least the steps (a) to (c) in this order
(2).
(a) a coating step of applying the resin composition according to claim 1 onto a substrate
(b) a solvent removing step of removing the solvent from the applied resin composition
(c) a heat treatment step of heat-treating the resin composition from which the solvent has been removed Characterized in that at least the steps (1) to (5) are included in this order
Method of manufacturing resin pattern.
(1) a coating step of applying the resin composition according to claim 1 onto a substrate
(2) a solvent removing step for removing the solvent from the applied resin composition
(3) an exposure step of exposing the resin composition from which the solvent has been removed to a patterned image by an actinic ray
(4) a developing step of developing the exposed resin composition with an aqueous developing solution
(5) Heat treatment process for heat-treating the developed resin composition A cured product obtained by the process for producing a cured product according to claim 16 or the process for producing a resin pattern according to claim 17. An optical member obtained by the method for producing a cured product according to claim 16 or the resin pattern production method according to claim 17.