KR20210121169A - Photosensitive resin composition, polymer, pattern, color filter, black matrix, display device and image pickup device - Google Patents

Abstract

It has a 1st structural unit represented by General formula (1), an acid value is 70-300 mgKOH/g, The photosensitive resin composition containing the polymer whose double bond equivalent is 100-500 g/mol. Moreover, it has a 1st structural unit represented by General formula (1), an acid value is 70-300 mgKOH/g, The polymer whose double bond equivalent is 100-500 g/mol. In the general formula (1), R ^D is a group containing a polymerizable carbon-carbon double bond.

Description

Photosensitive resin composition, polymer, pattern, color filter, black matrix, display device and image pickup device

The present invention relates to a photosensitive resin composition, a polymer, a pattern, a color filter, a black matrix, a display device, and an image pickup device.

DESCRIPTION OF RELATED ART A display apparatus (liquid crystal display etc.) and an imaging element (CCD, CMOS, etc.) are equipped with a color filter and a black matrix normally.

A photosensitive resin composition is used for formation of a color filter or a black matrix in many cases. Patterns, such as a color filter and a black matrix, are formed on a board|substrate by specifically forming a photosensitive resin film on a board|substrate with the photosensitive resin composition of photocurable property, and exposing and developing the film|membrane.

Patent Document 1 contains an acid group, a polymerizable unsaturated group and a blocked isocyanate group in a molecule, an acid value of 20 to 300 mgKOH/g, an unsaturated group equivalent of 100 to 4,000 g/mol, and a blocked isocyanate group Curable polymers having an equivalent weight of 400 to 6,000 g/mol are described. Moreover, forming a color filter using this curable polymer is described.

It is described in patent document 2 that a weight average molecular weight uses 1000-6000, acid value 80-200 mgKOH/g, and ethylenically unsaturated bond equivalent uses binder resin whose ethylenically unsaturated bond equivalent is 500 or less, and forms a black matrix.

In patent document 3, with respect to 1 mol of carboxyl groups in the copolymer formed by radical polymerization of the ethylenically unsaturated monomer of food 70-120 which does not have a carboxyl group, and the ethylenically unsaturated monomer containing a carboxyl group-containing ethylenically unsaturated monomer, an epoxy group containing The photosensitive resin obtained by making 0.2-0.9 mol of epoxy groups in an ethylenically unsaturated monomer react is described. Moreover, the photosensitive composition containing this photosensitive resin is described. Further, it is described that a color filter is formed using this photosensitive composition.

In patent document 3, the acid value of photosensitive resin becomes like this. Preferably it is described as 20-200 mgKOH/g. Moreover, the double bond equivalent of photosensitive resin becomes like this. Preferably it is described as 300-1000.

In Patent Document 4, in a carboxyl group-containing polymer represented by a specific general formula, (i) a compound having a carboxylic acid-reactive group and an ethylenically unsaturated group, or (ii) a compound having a carboxylic acid-reactive group and a silicon-based functional group, Alkali-soluble resin obtained by making it react, and the photosensitive resin composition containing this alkali-soluble resin are described. Moreover, forming a color filter using this photosensitive resin composition is described.

In Patent Document 4, the acid value of the alkali-soluble resin is preferably 25 to 100 mgKOH/g, and the ethylenically unsaturated group equivalent is preferably 50 to 400.

Patent Document 1: International Publication No. 2014/141731 Patent Document 2: Japanese Patent Application Laid-Open No. 2015-197619 Patent Document 3: Japanese Patent Application Laid-Open No. 2011-33951 Patent Document 4: Japanese Patent Application Laid-Open No. 2007-264433

When a pattern is formed using a photosensitive resin composition, especially a negative photosensitive resin composition, the ease of photocuring (that is, sensitivity) of the exposed part and the ease of dissolving the unexposed part in a developer solution (developability) are trade-offs. easy to be in a relationship

In particular, in recent years, against the background of further complexity and miniaturization of liquid crystal display devices and solid-state imaging devices, it is required to achieve both sensitivity and developability at a high level.

The present inventors examined this time as one objective of providing the photosensitive resin composition with which a sensitivity and developability were compatible.

MEANS TO SOLVE THE PROBLEM The present inventors completed the invention provided below, as a result of earnest examination.

According to the present invention, the following is provided.

One.

The photosensitive resin composition which has a 1st structural unit represented by the following general formula (1), is an acid value of 70-300 mgKOH/g, and contains the polymer whose double bond equivalent is 100-500 g/mol.

[Formula 1]

In General Formula (1), R ^D is a group containing a polymerizable carbon-carbon double bond.

2.

1. As the photosensitive resin composition as described in,

The photosensitive resin composition in which the said 1st structural unit contains the structural unit in which R ^D is a group containing two or more polymerizable carbon-carbon double bonds.

3.

1. or 2. as the photosensitive resin composition as described in,

wherein the first structural unit comprises a structural unit in which R ^D is a group containing two or more polymerizable carbon-carbon double bonds and a structural unit in which R ^D is a group containing only one polymerizable carbon-carbon double bond, A photosensitive resin composition.

4.

The photosensitive resin composition according to any one of 1. to 3.,

The photosensitive resin composition in which the said polymer further contains the 2nd structural unit represented by a following formula (MA).

[Formula 2]

5.

1. The photosensitive resin composition in any one of 4.

The photosensitive resin composition in which the said polymer further contains the structural unit which has a cyclic hydrocarbon skeleton.

6.

1. The photosensitive resin composition in any one of 5., Comprising:

The photosensitive resin composition whose ratio of the said 1st structural unit in all the structural units of the said polymer is 10-40 mol%.

7.

The photosensitive resin composition according to any one of 1. to 6.

The photosensitive resin composition whose weight average molecular weights of the said polymer are 6,000-25,000.

8.

The photosensitive resin composition according to any one of 1. to 7.

A photosensitive resin composition further comprising a colorant.

9.

The photosensitive resin composition according to any one of 1. to 7.

The photosensitive resin composition further comprising a light-shielding agent.

10.

A polymer having a first structural unit represented by the following general formula (1), an acid value of 70 to 300 mgKOH/g, and a double bond equivalent of 100 to 500 g/mol.

[Formula 3]

In General Formula (1), R ^D is a group containing a polymerizable carbon-carbon double bond.

11.

As the polymer described in 10.,

The first structural unit is ^{a polymer including a structural unit in which R D} is a group containing two or more polymerizable carbon-carbon double bonds.

12.

As the polymer according to 10. or 11.,

Wherein the first structural unit, R ^D is the polymerization of two or more carbon-polymer comprising a group structure unit containing a carbon-carbon double bond is a group structure comprising a carbon-carbon double bond units and, R ^D single polymerizable carbon .

13.

As the photosensitive resin composition in any one of 10.-12.,

The polymer further containing the 2nd structural unit represented by the following formula (MA).

[Formula 4]

14.

The polymer according to any one of 10. to 13.,

A polymer further comprising a structural unit having a cyclic hydrocarbon skeleton.

15.

The polymer according to any one of 10. to 14.,

The polymer whose ratio of the said 1st structural unit in all the structural units is 10-40 mol%.

16.

The polymer according to any one of 10. to 15.,

A polymer having a weight average molecular weight of 6,000 to 25,000.

17.

The pattern obtained using the photosensitive resin composition in any one of 1.-7.

18.

The color filter obtained using the photosensitive resin composition of 8.

19.

A display device provided with the color filter as described in 18.

20.

The imaging element provided with the color filter of 18.

21.

The black matrix obtained using the photosensitive resin composition of 9.

22.

The display device provided with the black matrix of 21.

23.

The imaging element provided with the black matrix of 21.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition with which a sensitivity and developability were compatible is provided. Moreover, the polymer suitable for manufacture of such a photosensitive resin composition is provided.

The above-mentioned and other objects, features, and advantages are made clearer by the preferred embodiment described below and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS It is a figure (cross-sectional view) which shows typically an example of the structure of a liquid crystal display device and/or a solid-state image sensor.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail, referring drawings.

In all drawings, the same code|symbol is attached|subjected to the same component, and description is abbreviate|omitted suitably.

In order to avoid complication, when there are a plurality of identical components in the same drawing, only one of them is attached and no reference numerals are attached to all of them in some cases.

The drawings are for illustrative purposes only. The shape, dimension ratio, etc. of each member in a drawing do not necessarily correspond to an actual article.

In this specification, "double bond" of "double bond equivalent" is a polymerizable carbon-carbon double bond.

In the present specification, the term “approximately” refers to including a range in consideration of manufacturing tolerances and assembly deviations, etc., unless otherwise explicitly stated.

In the present specification, the expression "a to b" in the description of the numerical range indicates a or more and b or less unless otherwise specified. For example, "1-5 mass %" means "1 mass % or more and 5 mass % or less".

In the description of a group (atomic group) in the present specification, the expression not describing whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The notation of "(meth)acryl" in this specification shows the concept containing both acryl and methacryl. The same is true for similar notations such as "(meth)acrylate".

The term "organic group" as used herein means an atomic group in which one or more hydrogen atoms have been removed from an organic compound, unless otherwise specified. For example, "monovalent organic group" represents an atomic group obtained by removing one hydrogen atom from any organic compound.

<Photosensitive resin composition>

The photosensitive resin composition of this embodiment has a 1st structural unit represented by General formula (1) below, an acid value is 70-300 mgKOH/g, and contains the polymer whose double bond equivalent is 100-500 g/mol.

In General Formula (1), R ^D is a group containing a polymerizable carbon-carbon double bond.

[Formula 5]

By manufacturing the photosensitive resin composition using the polymer mentioned above, the photosensitive resin composition with which a sensitivity and developability were compatible can be obtained. The reason can be explained as follows.

In addition, the present invention is not to be construed as being limited by the following description.

The structural unit represented by General formula (1) contains ^{"both" of the group (R D} in General formula) containing a polymerizable carbon-carbon double bond, and a carboxy group in one structural unit.

Because the polymerizable group and the carboxyl group are in the same structural unit, it is easy to design "both" of the amount of the polymerizable group and the amount of the carboxyl group in the polymer to a large value (with other resins such as (meth)acrylic resins, such a design is difficult. I think). This is suitable in terms of increasing the developability while increasing the sensitivity.

And, as the whole polymer, by designing an acid value to 70-300 mgKOH/g and designing a double bond equivalent to 100-500 g/mol, a sensitivity and developability can be made compatible at a high level.

That is, when the acid value of a polymer is 70 mgKOH/g or more, favorable developability can be acquired. Moreover, when a double bond equivalent is 500 g/mol or less, the sensitivity of a composition can be made high.

Moreover, when an acid value is too large, there exists a possibility that an exposure part will become easy to melt|dissolve at the time of development in an alkaline developing solution, the exposure amount required for photocuring will increase, or a pattern shape may become inadequate. Therefore, in this embodiment, the upper limit of the acid value is 300 mgKOH/g.

Moreover, when the double bond equivalent is excessively small (that is, when the density of double bonds in the polymer is excessively large), it tends to be difficult to dissolve the unexposed part or the low-exposed part at the time of development in an alkali developer, and at the time of development A residual film becomes easy to generate|occur|produce. Moreover, when a double bond equivalent is too small, molecular weight will increase excessively by crosslinking, and there is a concern, such as an excessive fall of solubility. Therefore, in the present embodiment, the lower limit of the double bond equivalent is 100 g/mol.

The acid value of a polymer is 70-300 mgKOH/g, Preferably it is 80-200 mgKOH/g.

The double bond equivalent of the polymer is 100 to 500 g/mol, preferably 200 to 470 g/mol.

By adjusting the acid value and/or double bond equivalent of a polymer, a sensitivity and developability can be made compatible at a still higher level.

If it is explained just in case, the acid value and the double bond equivalent can be obtained by spectral measurement or the like. For example, it can be obtained by the following procedure (refer to Examples more specifically).

(1) The area (integral value) of the peak corresponding to the hydrogen atom of a carboxy group or a hydrogen atom in the vicinity of a polymerizable carbon-carbon double bond is calculated|required from the <^{1>H-NMR chart of a polymer.}

(2) The amount of carboxyl groups and the amount of carbon-carbon double bonds are determined from the area of the peak derived from the standard substance based on the area determined in (1) as a reference.

(3) Convert the quantity of the carboxyl group calculated|required in (2) to an acid value (mgKOH/g). In addition, the quantity of the polymerizable carbon-carbon double bond calculated|required in (2) is converted into double bond equivalent (g/mol).

By appropriately designing the ratio of the structural unit represented by the general formula (1) in the polymer, the structure of R ^D in the general formula (1), and the number of polymerizable carbon-carbon double bonds contained in R ^D , the acid value of the polymer and the double The binding equivalent can be set to an appropriate value.

The component etc. which the photosensitive resin composition of this embodiment can contain are demonstrated below.

(Polymer)

As mentioned above, the photosensitive resin composition of this embodiment has a 1st structural unit represented by General formula (1), an acid value is 70-300 mgKOH/g, and contains a polymer whose double bond equivalent is 100-500 g/mol. do. In the general formula (1), R ^D may be any group as long as it is a group containing a polymerizable carbon-carbon double bond.

・First structural unit

The first structural unit ^{preferably includes a structural unit in which R D} is a group containing two or more polymerizable carbon-carbon double bonds. ^{In other words, part or all of R D} of the structural unit represented by the general formula (1) in the polymer is preferably a group containing two or more polymerizable carbon-carbon double bonds.

When R ^D contains two or more polymerizable carbon-carbon double bonds, the number ^{of polymerizable carbon-carbon double bonds in R D} is preferably 2-6, more preferably 2-5, even more preferably It is 3-5. ^{By adjusting the number of polymerizable double bonds which RD} contains, a sensitivity and developability can be made compatible at a higher level.

When R ^D comprises two or more polymerizable carbon-carbon double bonds, preferably at least one (more preferably all) of the two or more polymerizable double bonds is present at the terminus of ^{R D .} By setting it as such a structure, a polymerizable double bond becomes easy to react with the active chemical species which generate|occur|produced from a photoinitiator. Accordingly, it is possible to further improve the sensitivity.

When R ^D contains two or more polymerizable carbon-carbon double bonds, as an example, R ^D contains two or more (meth)acryloyl groups. More specifically, ^RD is 2-6, Preferably 2-5, More preferably, the (meth)acryloyl group of 3-5 is included. Moreover, for the further improvement of a sensitivity, it is preferable that a (meth)acryloyl group is an acryloyl group. This is because the acryloyl group not substituted with the methyl group reacts more easily with the active species generated from the photopolymerization initiator than the methacryloyl group.

When R ^D contains two or more (meth)acryloyl groups, R ^D may be, for example, a group represented by the following general formula (1b) or (1c).

[Formula 6]

In general formula (1b),

k is 2 or 3,

R is a hydrogen atom or a methyl group, a plurality of R may be the same or different,

X ¹ is a single bond, a group represented by alkylene or -ZX- of 1 to 6 carbon atoms (and Z is -O- or -OCO-, X is an alkylene group having 1 to 6 carbon atoms), and a plurality of X ¹ present may be the same or different,

X ¹ ' is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-) is,

X ² is a k+1 valent organic group having 1 to 12 carbon atoms.

R is preferably a hydrogen atom from the viewpoint of further improvement in sensitivity (easiness of polymerization) and the like.

Although 2 or 3 may be sufficient as k, from the point of the further improvement of the availability of a raw material and a sensitivity, Preferably it is 3.

When X ¹ is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched.

When X ¹ is an alkylene group having 1 to 6 carbon atoms, X ¹ is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, further preferably -CH ₂ -(methylene). group) is

X ¹ tooth When the group represented by -ZX- (Z is -O- or -OCO-, X is an alkylene group having 1 to 6 carbon atoms), the alkylene group having 1 to 6 carbon atoms in X may be linear or branched. .

Alkylene of 1 to 6 carbon atoms in the group X, preferably a straight chain alkylene group, more preferably a straight chain alkylene group having 1 to 3 carbon atoms, more preferably -CH ₂ -CH ₂ - (ethylene group) or —CH ₂ —CH(CH ₃ )—.

When X ¹ ′ is an alkylene group having 1 to 6 carbon atoms, the specific aspect thereof is the same as that of ^{X 1 .}

When X ¹ ' is a group represented by -X'-Z'-, specific aspects of X' are the same as those of X above.

Examples of the k+1 valent organic group having 1 to 12 carbon atoms of X ^{2 include any group obtained by removing k+1 hydrogen atoms from any organic compound.} The "arbitrary organic compound" herein is, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, and more preferably 100 or less.

X ² is, for example, a group obtained by removing k+1 hydrogen atoms from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is the group which removed k+1 hydrogen atoms from a C1-C3 linear hydrocarbon. In addition, the hydrocarbon here may also contain the oxygen atom (For example, an ether bond, a hydroxyl group, etc.). Moreover, it is preferable that a hydrocarbon is a saturated hydrocarbon.

As another aspect, X ² may also contribute including a cyclic structure. As group containing a cyclic structure, the group containing an alicyclic structure, the group containing a heterocyclic structure (for example, isocyanuric acid structure), etc. are mentioned.

[Formula 7]

In general formula (1c),

k, R, X ¹ and X ² each have the same meaning as R, k, X ¹ and X ^{2 in the} general formula (1b), and a plurality of R may be the same as or different from each other, and a plurality of X ¹ may be the same or different,

X ³ is a divalent organic group having 1 to 6 carbon atoms,

X ⁴ and X ⁵ are each independently a single bond or a divalent organic group having 1 to 6 carbon atoms,

X ⁶ is a divalent organic group having 1 to 6 carbon atoms.

Specific aspects and preferred aspects of R, k, X ¹ and X ² are the same as those described in the general formula (1b).

Examples of the divalent organic group having 1 to 6 carbon atoms for X ³ and X ⁶ include a group obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to 6 carbon atoms. In addition, the hydrocarbon here may also contain the oxygen atom (For example, an ether bond, a hydroxyl group, etc.). Moreover, it is preferable that a hydrocarbon is a saturated hydrocarbon.

Examples of X ⁴ and X ⁵ in the divalent organic group having 1 to 6, there may be mentioned a straight chain or branched alkylene group. The straight-chain or branched alkylene group preferably has 1 to 3 carbon atoms.

The first structural unit preferably includes a structural unit in which R ^D is a group containing two or more polymerizable carbon-carbon double bonds, and a structural unit in which R ^D is a group containing only one polymerizable carbon-carbon double bond. do. As another expression, Preferably, among the structural units represented by the general formula (1) in the polymer, R ^D in some structural units is a group containing two or more polymerizable carbon-carbon double bonds, and the general formula (1) in the polymer ), R ^D in the remaining structural units is a group containing only one polymerizable carbon-carbon double bond.

By designing a polymer in this way, it becomes easy to obtain still more favorable developability, raising a sensitivity.

The specific aspect of "the structural unit in which R ^D is a group containing two or more polymerizable carbon-carbon double bonds" is as described above (in the general formula (1), R ^D is the general formula (1b) or (1c) ), etc.).

In the " ^{structural unit in which R D} is a group comprising only one polymerizable carbon-carbon double bond", the polymerizable double bond is preferably present at the terminus of ^{R D .} In addition, the R ^D includes, in one aspect, the one group to the (meth) acrylate. From a viewpoint of the further improvement of a sensitivity, it is preferable that the (meth)acryloyl group is an acryloyl group. More specifically, R ^D may be a group represented by the following general formula (2a).

[Formula 8]

In the general formula (2a), X ¹⁰ is a divalent organic group, and R is a hydrogen atom or a methyl group.

The total number of carbon atoms of X ¹⁰ is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 10.

As the ^{divalent organic group of X 10} , for example, an alkylene group is preferable. A part of -CH ₂ - in this alkylene group may be an ether group (-O-). Although linear or branched form may be sufficient as an alkylene group, it is more preferable that it is linear.

As the divalent organic group of X ¹⁰ , more preferably, it is a linear alkylene group having 3 to 6 carbon atoms in total. Suitably by selecting the number of carbon atoms in X ¹⁰ (equivalent to the "length" of X ^10), groups represented by the formula (2a) is likely to further participate in the curing reaction. Therefore, the sensitivity can be further raised.

The divalent organic group for X ¹⁰ (e.g. alkylene group) is optionally substituted with any substituent. As a substituent, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, etc. are mentioned.

Moreover, arbitrary contributions other than an alkylene group may be sufficient as the divalent organic group of ^X<10>. For example, a divalent contribution constituted by connecting one or more groups selected from an alkylene group, a cycloalkylene group, an arylene group, an ether group, a carbonyl group, a carboxy group, and the like may be acceptable.

The proportion of the first structural unit in the total structural units of the polymer is preferably 10 to 40 mol%, more preferably 15 to 35 mol%.

Further, the polymer is a first structural unit, a structural unit in which R ^D is a group containing two or more polymerizable carbon-carbon double bonds and a structural unit in which R ^D is a group containing only one polymerizable carbon-carbon double bond. When both are included, the molar ratio of the former to the latter is preferably 5:95 to 50:50, more preferably 10:90 to 40:60. By adjusting this ratio appropriately, it is easy to make a sensitivity and developability compatible still more highly.

Here, the former: latter molar ratio can be calculated|required as follows, for example.

In the polymer, the amount of the former is X ₁ (mol/g), the amount of the latter is X ₂ (mol/g), the amount of carboxyl groups is C (mol/g), and the amount of polymerizable carbon-carbon double bonds is D (mol/g). In addition, it is said that the former contains n polymerizable carbon-carbon double bonds.

Both the former and the latter have one carboxyl group. Thus, X ₁ +X ₂ =C is written (assuming that the polymer contains no other structural unit containing a carboxyl group).

In addition, with respect to the amount of a polymerizable carbon-carbon double bond, n*X ₁ +X ₂ =D is written (assuming that the polymer does not contain other structural units containing a polymerizable double bond).

C and D can be known from the peak area obtained by NMR measurement. In addition, n is determined by the chemical structure of a raw material. Therefore, by solving these two equations for the unknowns X ₁ and X ₂ as simultaneous equations, the molar ratio of the former to the latter can be obtained.

In addition _{, from the sum of X 1} and X _2, the number of moles (mol/g) of each structural unit contained in the raw material polymer (described later), and the molecular weight of the monomer underlying each structural unit contained in the raw material polymer, the overall structure of the polymer The ratio of the 1st structural unit (total when there are a plurality of 1st structural units) in a unit can be calculated|required.

・Second structural unit

It is preferable that a polymer further contains the 2nd structural unit represented by a formula (MA) below.

The second structural unit can be ring-opened with an alkali developer. Since two carboxyl groups generate|occur|produce when ring-opening, it is thought that the further improvement of developability is achieved.

[Formula 9]

When a polymer contains the structural unit represented by Formula (MA), the ratio of the structural unit represented by Formula (MA) in all the structural units of a polymer becomes like this. Preferably it is 1-25 mol%, More preferably, it is 3-20 mol%. am.

· Solubility adjustment structural unit

The polymer may contain one or two or more of the structural units represented by the following general formulas (a2-1), (a2-2) or (a2-3). By including such a structural unit in a polymer, adjustment of the solubility with respect to developability, adjustment of the solubility with respect to an organic solvent, etc. are possible.

In general formulas (a2-1) and (a2-2), R ₁₄ , R ₁₅ and R ₁₆ are each independently an organic group having 1 to 30 carbon atoms.

[Formula 10]

The organic group having 1 to 30 carbon atoms constituting R ₁₄ , R _{15 ,} and R ₁₆ may contain any one or more of O, N, S, P, and Si in the structure. Further, _{the organic group constituting R 14} , R ₁₅ and R ₁₆ may not contain an acidic functional group. Thereby, control of an acid value can be made easily.

Examples of the organic group constituting R ₁₄ , R ₁₅ and R ₁₆ include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, and a heterocyclic group. .

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, hep. A tyl group, an octyl group, a nonyl group, a decyl group, etc. are mentioned.

As an alkenyl group, an allyl group, a pentenyl group, a vinyl group, etc. are mentioned, for example.

As an alkynyl group, ethaneyl group etc. are mentioned, for example.

As an alkylidene group, a methylidene group, an ethylidene group, etc. are mentioned, for example.

As an aryl group, a phenyl group, a naphthyl group, anthracenyl group, etc. are mentioned, for example.

As an aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned, for example.

As an alkaryl group, a tolyl group, a xylyl group, etc. are mentioned, for example.

Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

As a heterocyclic group, an epoxy group, oxetanyl group, etc. are mentioned, for example.

In these alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, and heterocyclic groups, one or more hydrogen atoms may be substituted with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Among them, a haloalkyl group in which at least one hydrogen atom of the alkyl group is substituted with a halogen atom is preferable.

Structural unit having a cyclic hydrocarbon skeleton

The polymer preferably includes a structural unit having a cyclic hydrocarbon skeleton. By the rigid structure of a cyclic hydrocarbon skeleton, the heat resistance of a cured film at the time of hardening the photosensitive resin composition, mechanical properties, etc. can be improved, for example.

The structural unit having a cyclic hydrocarbon skeleton is, for example, derived from the following monomers.

Cyclic olefin monomer. Specifically, norbornene, norbornadiene, bicyclo[2.2.1]-hept-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene , 5-Butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl)-2-norbornene , 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethylidene-2 norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, etc. A monomer having a nene skeleton or a norbornadiene skeleton.

A monomer having an indene skeleton or an acenaphthylene skeleton, such as indene, 2-methylindene, 3-methylindene, and acenaphthylene.

1,5,9-cyclododecatriene, cis-trans-trans-1,5,9-cyclododecatriene, trans-trans-trans-1,5,9-cyclododecatriene, trans- A monomer having a triene structure, such as cis-cis-1,5,9-cyclododecatriene and cis-cis-cis-1,5,9-cyclododecatriene.

A monomer having a styrene skeleton such as styrene, vinyltoluene, hydroxystyrene, acetoxystyrene, or α-methylstyrene.

N-cycloalkyl maleimides such as N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-norbornylmaleimide, N-cyclohexylmethylmaleimide and N-cyclopentylmethylmaleimide.

N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N -N-aryl maleimides, such as nitrophenyl maleimide.

As the structural unit having a cyclic hydrocarbon skeleton, a structural unit derived from a cyclic olefin monomer is preferable, and a structural unit derived from a monomer having a norbornene skeleton or norbornadiene skeleton is more preferable. More specifically, it is preferable that the structural unit which has a cyclic hydrocarbon skeleton is what is represented by General formula (NB) below.

[Formula 11]

Of the general formula (NB),

R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms,

a ₁ is 0, 1 or 2.

^{Examples of the organic group having 1 to 30 carbon atoms for R 1} , R ² , R ³ and R ^{4 in} the general formula (NB) include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, and an alkane group. a ryl group, a cycloalkyl group, an alkoxy group, a heterocyclic group, a carboxyl group, etc. are mentioned.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group , an octyl group, a nonyl group, a decyl group, and the like.

As an alkenyl group, an allyl group, a pentenyl group, a vinyl group, etc. are mentioned, for example.

As an alkynyl group, ethaneyl group etc. are mentioned, for example.

As an alkylidene group, a methylidene group, an ethylidene group, etc. are mentioned, for example.

Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group.

As an aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned, for example.

As an alkaryl group, a tolyl group, a xylyl group, etc. are mentioned, for example.

Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

Examples of the alkoxy group include a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, n-pentyloxy group, A neopentyloxy group, n-hexyloxy group, etc. are mentioned.

As a heterocyclic group, an epoxy group, an oxetanyl group, etc. are mentioned, for example.

^{As R 1} , R ² , R ³ and R ^{4 in the} general formula (NB), hydrogen or an alkyl group is preferable, and hydrogen is more preferable.

The hydrogen atom in the C1-C30 organic group of R<^1> , R<^2> , R<^3>, and R<^{4> may be substituted by arbitrary atomic groups.} For example, it may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, etc. More specifically, ^{as the organic group having 1 to 30 carbon atoms for R 1} , R ² , R ^{3 ,} and R ⁴ , an alkyl fluoride group or the like may be selected.

In the general formula (NB), a ₁ is preferably 0 or 1, more preferably 0.

When the polymer contains a structural unit having a cyclic hydrocarbon skeleton, the amount is preferably 10 to 90 mol%, more preferably 30 to 70 mol%, still more preferably 40 to 60 mol%, based on the total structural units of the polymer. am. By adjusting this ratio appropriately, it is easy to acquire the further effect (for example, the heat resistance improvement and mechanical property improvement at the time of setting it as a cured film) making a sensitivity and developability compatible.

In addition, from the viewpoint of overall performance and cost, the polymer is different from the first structural unit as an essential structural unit, the second structural unit as an optional structural unit, and a structural unit having a cyclic hydrocarbon skeleton. It is preferable that it does not contain "structural unit" or that it contains a small amount even if it does. Specifically, the proportion of "other structural units" in the polymer is preferably 0 to 20 mol%, more preferably 0 to 10 mol%.

The weight average molecular weight of a polymer becomes like this. Preferably it is 6,000-25,000, More preferably, it is 7,000-20,000. By appropriately adjusting the weight average molecular weight, the solubility in an alkali developing solution, the solubility in an organic solvent, and the like can be appropriately adjusted.

Polymer dispersion degree (weight average molecular weight Mw/number average molecular weight Mn) becomes like this. Preferably it is 1.0-5.0, More preferably, it is 1.0-4.0, More preferably, it is 1.0-3.0. By appropriately adjusting the degree of dispersion, the physical properties of the polymer can be made homogeneous, which is preferable.

These values can be calculated|required by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

The polymer may be manufactured (synthesized) by any method. For example,

A preparatory step of preparing a raw material polymer containing at least a structural unit represented by the above formula (MA);

- A polymer can be manufactured by the reaction process of making the raw material polymer and the compound which has a hydroxyl group and a polymerizable carbon-carbon double bond react in presence of a basic catalyst.

Hereinafter, a method for preparing (synthesizing) a polymer by the above-described preparation process and reaction process will be described in more detail. Although the description takes as an example the synthesis|combination of the polymer containing the structural unit represented by General formula (1) and the structural unit represented by General formula (NB), this does not lose the generality of a polymer manufacturing method. For example, a polymer including a structural unit represented by the general formula (1) and a structural unit (copolymerized unit) other than the general formula (NB) can also be synthesized by a procedure similar to the description below.

・Preparation process

The raw material polymer can be obtained, for example, by polymerization (addition polymerization) of a monomer represented by the following general formula (NB-m) and maleic anhydride.

^{The definitions of R 1} , R ² , R ³ and R ⁴ and a _{1 in} the general formula (NB-m) are the same as those in the general formula (NB). It is the same also about a preferable aspect.

[Formula 12]

Examples of the monomer represented by the general formula (NB-m) include bicyclo[2.2.1]-hept-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl -2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl) -2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2 -norbornene, 2-acetyl-5-norbornene, 5-norbornene-2-carboxylate methyl, 5-norbornene-2,3-dicarboxylic acid anhydride, norbornadiene, etc. are mentioned.

At the time of superposition|polymerization, only 1 type may be used for the monomer represented by General formula (NB-m), and may be used in combination of 2 or more type.

Although the method of polymerization is not limited, Radical polymerization using a radical polymerization initiator is preferable.

As a polymerization initiator, an azo compound, an organic peroxide, etc. can be used, for example.

Specifically as the azo compound, azobisisobutyronitrile (AIBN), dimethyl-2,2'-azobis(2-methylpropionate), 1,1'-azobis(cyclohexanecarbonitrile) ) (ABCN) and the like.

Examples of the organic peroxide include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP).

About a polymerization initiator, only 1 type may be used and may be used in combination of 2 or more type.

As a polymerization solvent, organic solvents, such as diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, can be used, for example. A single solvent may be sufficient as a polymerization solvent, and a mixed solvent may be sufficient as it.

Addition polymerization is advanced by dissolving the monomer represented by general formula (NB-m), maleic anhydride, and a polymerization initiator in a solvent, injecting|throwing-in to a reaction container, and heating after that. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 5 to 20 hours.

It is preferable that the molar ratio of the monomer represented by General formula (NB-m) and maleic anhydride at the time of inject|throwing-in to a reaction container is 0.5:1-1:0.5. From the viewpoint of molecular structure control, the molar ratio is preferably 1:1.

By the above process, a "raw material polymer" can be obtained.

The raw material polymer may be any of a random copolymer, an alternating copolymer, a block copolymer, a periodic copolymer, and the like. Typically, it is a random or alternating copolymer (generally, maleic anhydride is known as a monomer with strong alternating copolymerizability).

After the synthesis of the raw material polymer, a step of removing low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators may be performed.

Specifically, the synthesized raw material polymer and the organic layer containing the low molecular weight component are concentrated, and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. And this solution is mixed with poor solvents, such as methanol, and a monomer is precipitated. The purity of the raw material polymer can be improved by filtering and drying this precipitate.

・Reaction process

By reacting the raw material polymer obtained in the preparation step with a compound having a hydroxyl group and a polymerizable carbon-carbon double bond in the presence of a basic catalyst, the structural unit of formula (MA) contained in the raw material polymer is ring-opened. Thereby, the structural unit of General formula (1) is formed.

More specifically, first, a polymer solution in which a raw material polymer is dissolved in a suitable organic solvent is prepared.

Examples of the organic solvent that can be used herein include methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), tetrahydrofuran ( A single solvent or mixed solvent, such as THF), is mentioned. Of course, the solvent is not limited thereto, and various organic solvents used in the synthesis of organic compounds or polymers can be used.

Next, to this polymer solution, a compound having a hydroxyl group and a polymerizable carbon-carbon double bond is added. Also, a basic catalyst is added. And mix appropriately to make a uniform solution.

As a compound which has a hydroxyl group and a polymerizable carbon-carbon double bond, the compound containing 1 or 2 or more (meth)acryloyl groups and a hydroxyl group is mentioned, for example.

By using a compound (polyfunctional compound) containing two or more (meth)acryloyl groups and a hydroxyl group, in the polymer, R ^D in the general formula (1) contains two or more polymerizable carbon-carbon double bonds A group structural unit may be introduced.

On the other hand, by using a compound (monofunctional compound) containing only one (meth)acryloyl group and a hydroxyl group, in the polymer, R ^D in the general formula (1) is only one polymerizable carbon-carbon double Structural units may be introduced which are groups containing bonds.

By using both of these polyfunctional compounds and monofunctional compounds, as the first structural unit, a structural unit in which R ^D is a group containing two or more polymerizable carbon-carbon double bonds, and R ^D is only one polymerizable carbon- Both of the structural units of the group containing a carbon double bond can be introduced into the polymer. However, in terms of steric hindrance, monofunctional compounds tend to react more easily with polymers than polyfunctional compounds, so in the reaction step, it is preferable to "lottery" without introducing the monofunctional compound into the reaction system from the beginning. .

As "a compound containing two or more (meth)acryloyl groups and a hydroxyl group", specifically, the compound represented by the following general formula (1b-m) or the compound represented by the following general formula (1c-m) is mentioned have.

^{The definitions and specific aspects of k, R, X 1} , X ¹ ' and X ^{2 in} the general formula (1b-m) are the same as in the general formula (1b).

^{The definitions and specific aspects of k, R, X 1 ,} X ² , X ³ , X ⁴ , X ⁵ and X ^{6 in} the general formula (1c-m) are the same as in the general formula (1c).

[Formula 13]

[Formula 14]

What can be preferably used as a compound containing two or more (meth)acryloyl groups and a hydroxyl group is shown below. Moreover, what made some or all of the acryloyl groups of the compound shown below a (meth)acryloyl group (or vice versa) etc. can be used.

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

In addition, as "a compound containing only one (meth)acryloyl group and a hydroxyl group", the compound represented by the following general formula (2a-m) is mentioned, for example.

In the general formula (2a-m), ^{the definitions and specific embodiments of X 10} and R are the same as in the general formula (2a).

[Formula 20]

As a specific example of the compound represented by General formula (2a-m), 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1, 4- cyclohexane dimethanol mono(meth)acryl Rate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl -2-hydroxyethyl phthalic acid etc. are mentioned.

After the reaction step, the reaction is stopped by diluting the reaction solution with an organic solvent and/or adding an acid to neutralize the basic catalyst.

A polymer can be obtained by the above process.

For reference, in the reaction step, by appropriately adjusting the amount of the compound having a hydroxyl group and a polymerizable carbon-carbon double bond, all maleic anhydride structures in the raw material polymer are not ring-opened, and in the final polymer The structure of formula (MA) will be included.

Further, in the reaction step, by reacting water, alcohol, or other suitable substance with the maleic anhydride structure in the raw material polymer, according to the general formula (a2-1), (a2-2) or (a2-3) The structural unit which appears can be introduce|transduced in a polymer.

In order to remove unnecessary components other than a desired polymer, it is further preferable to perform the following process suitably.

First, as described above, the reaction solution diluted with an organic solvent and added with an acid (eg, formic acid) is strongly stirred for at least 3 minutes with a separatory funnel. This is stopped for 30 minutes or more, divided into an organic phase and a water phase, and an aqueous phase is removed. In this way, an organic solution of the polymer is obtained.

To the organic solution of the obtained polymer, an excess amount of toluene is added to reprecipitate the polymer. Further, the polymer powder obtained by reprecipitation is further washed several times with toluene.

In addition, the operation of washing the obtained polymer powder with ion-exchanged water is repeated several times (about 3 times) in order to remove the formic acid and the basic catalyst.

A high-purity polymer can be obtained by drying the polymer powder after washing|cleaning with ion-exchange water at 30-60 degreeC for 16 hours or more, for example.

(Photoinitiator)

The photosensitive resin composition of this embodiment, Preferably, a photoinitiator is included.

As long as the component which generate|occur|produces by light irradiation is a thing which makes the polymerizable double bond contained in the structural unit of General formula (1) of a polymer react, arbitrary things can be used as a photoinitiator. The photopolymerization initiator may be, for example, a photoradical polymerization initiator, a photocationic polymerization initiator, or a photoanionic polymerization initiator.

Moreover, a photoinitiator generate|occur|produces the chemical species which are active by irradiation with ultraviolet light, more specifically, g-ray|wire, i-ray|ray etc. typically.

From a viewpoint of further sensitization, etc., Preferably, a photoinitiator is a photoradical polymerization initiator.

It does not specifically limit as a photoradical polymerization initiator, A well-known thing can be used suitably. For example, the following are mentioned.

2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one , 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2- Hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-dimethylamino-2-[(4-methylphenyl)methyl]-1-[4-(4-mo Alkylphenone compounds, such as polynyl)phenyl]-1-butanone.

Benzophenone compounds such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 2-carboxybenzophenone.

Benzoin compounds, such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone compound.

2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s- Triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(tri A halomethylated triazine-based compound such as chloromethyl)-s-triazine.

2-Trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3 Halomethylated oxadiazole compounds such as ,4-oxadiazole, 4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl) -4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5' -Biimidazole compounds, such as tetraphenyl-1,2'- biimidazole.

1,2-Octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl- Oxime ester compounds, such as 9H-carbazol-3-yl] ethanone oxime.

A titanocene-based compound such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium.

Benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid.

acridine-based compounds such as 9-phenylacridine.

The photosensitive resin composition may contain only 1 type, and may contain 2 or more types of photoinitiators.

The usage-amount of a photoinitiator is 1-20 mass parts with respect to 100 mass parts of polymers, Preferably it is 3-10 mass parts.

(solvent)

The photosensitive resin composition of this embodiment contains a solvent typically. Thereby, a uniform photosensitive resin film can be formed on the surface of various board|substrates.

As the solvent, an organic solvent is preferably used. Specifically, one or two or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, and the like can be used.

Examples of the solvent include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma butyrolactone (GBL), N -Methylpyrrolidone (NMP), methyl-n-amylketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclo hexanone, or a mixture thereof.

The usage-amount of a solvent is not specifically limited. For example, the density|concentration of a non-volatile component is 10-70 mass %, for example, Preferably it is used in the quantity which becomes 15-60 mass %.

(crosslinking agent)

The photosensitive resin composition of this embodiment can contain a crosslinking agent.

The crosslinking agent is not particularly limited as long as it can crosslink the polymer by the action of active chemical species generated from the photopolymerization initiator (which can chemically bond with the polymer).

The crosslinking agent may not chemically bond only with the polymer, but may react with each other to form a bond.

The crosslinking agent is, for example, preferably a polyfunctional compound having two or more polymerizable double bonds in one molecule, and more preferably a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups in one molecule. (However, the crosslinking agent does not correspond to the above-mentioned polymer). It is preferable to use the crosslinking agent which has a crosslinkable group (polymerizable double bond) and the same kind of crosslinkable group which a polymer has from points, such as uniform sclerosis|hardenability and further improvement of a sensitivity.

Although there is no upper limit in particular of the functional number (the number of polymerizable double bonds) per molecule of crosslinking agent, For example, it is 8 or less, Preferably, it is 6 or less.

Specific examples of the crosslinking agent include the following.

Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di (meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth) Acrylate, trimethylol propane tri (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide addition trimethylol propane tri (meth) acrylate, ethylene oxide addition ditrimethylol propane tetra (meth) acrylate, ethylene Oxide addition pentaerythritol tetra(meth)acrylate, ethylene oxide addition dipentaerythritol hexa(meth)acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, propylene oxide addition ditrimethylolpropane Tetra (meth) acrylate, propylene oxide addition pentaerythritol tetra (meth) acrylate, propylene oxide addition dipentaerythritol hexa (meth) acrylate, ε-caprolactone addition trimethylolpropane tri (meth) acrylate , ε-caprolactone addition ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone addition pentaerythritol tetra(meth)acrylate, ε-caprolactone addition dipentaerythritol hexa(meth)acrylate, etc. of polyfunctional (meth)acrylates.

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol Divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylol propane trivinyl ether, ditrimethylol propane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide addition trimethylol propane trivinyl ether, ethylene oxide addition ditrimethylol propane Polyfunctional vinyl ethers, such as tetravinyl ether, ethylene oxide addition pentaerythritol tetravinyl ether, and ethylene oxide addition dipentaerythritol hexavinyl ether.

(meth)acrylic acid 2-vinyloxyethyl, (meth)acrylic acid 3-vinyloxypropyl, (meth)acrylic acid 1-methyl-2-vinyloxyethyl, (meth)acrylic acid 2-vinyloxypropyl, (meth)acrylic acid 4- Vinyloxybutyl, (meth)acrylic acid 4-vinyloxycyclohexyl, (meth)acrylic acid 5-vinyloxypentyl, (meth)acrylic acid 6-vinyloxyhexyl, (meth)acrylic acid 4-vinyloxymethylcyclohexylmethyl, (meth)acrylic acid ) acrylic acid p-vinyloxymethylphenylmethyl, (meth)acrylic acid 2-(vinyloxyethoxy)ethyl, (meth)acrylic acid 2-(vinyloxyethoxyethoxyethoxy)ethyl, containing vinyl ether groups (meth) Acrylic acid esters.

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol Diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylol propane triallyl ether, ditrimethylol propane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide addition trimethylol propane triallyl ether, ethylene oxide addition ditrimethylol propane Polyfunctional allyl ethers, such as tetraallyl ether, ethylene oxide addition pentaerythritol tetraallyl ether, and ethylene oxide addition dipentaerythritol hexaallyl ether.

Allyl group-containing (meth)acrylic acid esters, such as (meth)acrylic acid allyl.

Tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide addition tri (acryloyloxyethyl) isocyanurate, alkylene oxide addition tri ( Polyfunctional (meth)acryloyl group containing isocyanurates, such as methacryloyloxyethyl) isocyanurate.

Polyfunctional allyl group-containing isocyanurates, such as triallyl isocyanurate.

Polyfunctional isocyanate, such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, and hydroxyl groups, such as (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl Polyfunctional urethane (meth)acrylates obtained by reaction of (meth)acrylic acid esters.

Polyfunctional aromatic vinyls, such as divinylbenzene.

Among them, trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and ditrimethylolpropanetetra 6 functional (meth)acrylates, such as tetrafunctional (meth)acrylates, such as (meth)acrylate, and dipentaerythritol hexa(meth)acrylate, are preferable.

When the photosensitive resin composition contains a crosslinking agent, the photosensitive resin composition may contain only 1 type and may contain 2 or more types of crosslinking agents.

When the photosensitive resin composition contains a crosslinking agent, what is necessary is just to set the quantity suitably according to the objective and a use. As an example, the quantity of a crosslinking agent is 30-70 mass parts normally with respect to 100 mass parts of polymers, Preferably it can be 40-60 mass parts.

(coloring agent)

The photosensitive resin composition of this embodiment can contain a coloring agent. When a composition contains a coloring agent, it can use suitably as a formation material of the color filter of a display apparatus or an imaging element.

As the colorant, various pigments or dyes can be used.

As a pigment, an organic pigment and an inorganic pigment can be used.

Examples of the organic pigment include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perrinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, Anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, xanthene pigments, pyromethene pigments, dye lake pigments, etc. can be used.

Examples of inorganic pigments include white and constitutional pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), chromatic pigments (yellow lead, cadmium series, chromium vermillion, nickel titanium, chromium titanium, yellow oxide) Iron, bengala, zinc chromate, rostrum, ultramarine blue, royal blue, cobalt blue, chromium green, chromium oxide, bismuth vanadate, etc.), brilliance pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.) can be used.

As dye, the well-known dye described in Unexamined-Japanese-Patent No. 2003-270428, Unexamined-Japanese-Patent No. 9-171108, Unexamined-Japanese-Patent No. 2008-50599, etc. can be used, for example.

As a colorant (particularly a pigment), according to the objective and a use, what has an appropriate average particle diameter can be used. In particular, when transparency like a color filter is requested|required, a small average particle diameter of 0.1 micrometer or less is preferable. On the other hand, when hiding properties such as paint are required, a large average particle diameter of 0.5 µm or more is preferable.

The colorant may be subjected to surface treatment such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, or wax coating depending on the purpose or use.

When the photosensitive resin composition contains a coloring agent, the photosensitive resin composition may contain only 1 type and may contain 2 or more types of coloring agents.

When the photosensitive resin composition contains a colorant, the amount thereof may be appropriately set depending on the purpose or use, but from the viewpoint of coexistence of the color concentration and dispersion stability of the colorant, etc., the total non-volatile components (components excluding the solvent) of the photosensitive resin composition , Preferably it is 3-70 mass %, More preferably, it is 5-60 mass %, More preferably, it is 10-50 mass %.

(Light-shielding agent)

The photosensitive resin composition of this embodiment can contain a light-shielding agent. When a composition contains a light-shielding agent, it can use suitably as a formation material of the black matrix of a display apparatus or an imaging element.

As a light-shielding agent, a well-known light-shielding agent in particular can be used without restriction|limiting. For example, black pigments, such as carbon black, bone black, graphite, iron black, and titanium black, can be used as a light-shielding agent.

When the photosensitive resin composition contains a light-shielding agent, the amount thereof may be appropriately set according to the purpose or use. , Preferably it is 3-70 mass %, More preferably, it is 5-60 mass %, More preferably, it is 10-50 mass %.

(Other ingredients)

The photosensitive resin composition of this embodiment may contain components other than the above according to various objectives and a requested|required characteristic.

As a component which may be included, for example, filler, binder resin other than the above-mentioned polymer, polyfunctional (meth)acrylate compound, acid generator, heat resistance improver, developing aid, plasticizer, polymerization inhibitor, ultraviolet absorber, antioxidant , a gloss remover, an antifoaming agent, a leveling agent, a surfactant, an antistatic agent, a dispersing agent, a slip agent, a surface modifier, a thixotropic agent, a silane coupling agent, and a polyhydric phenol compound.

<Pattern, color filter, black matrix, display device, imaging device, and method of manufacturing a display device or imaging device>

A film can be formed using the above-mentioned photosensitive resin composition, and the film|membrane can be exposed and developed, and a pattern can be formed. This pattern is applied, for example, to a color filter, a black matrix, or the like. A color filter can be obtained by forming a pattern specifically, using the photosensitive resin composition containing a coloring agent. Moreover, a black matrix can be obtained by forming a pattern using the photosensitive resin composition containing a light-shielding agent. And a display device (typically a liquid crystal display device) or an imaging device (typically a solid-state imaging device) provided with a color filter and/or a black matrix can be manufactured.

A typical procedure for forming a pattern will be described below.

・Formation of photosensitive resin film

For example, the photosensitive resin composition of this embodiment is apply|coated on arbitrary board|substrates, and it is made to dry as needed. Thereby, first, a photosensitive resin film is obtained.

The substrate is not particularly limited. For example, a glass substrate, a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, a copper clad laminated board etc. are mentioned.

The substrate may be a raw substrate or a substrate having electrodes and elements formed on the surface thereof. The board|substrate may be surface-treated for the improvement of adhesiveness.

The coating method of the photosensitive resin composition is not specifically limited. Application|coating can be performed by rotation application|coating using a spinner, spray application|coating using a spray coater, immersion, printing, roll coating, an inkjet method, etc.

Drying of the photosensitive resin composition apply|coated on the board|substrate is typically performed by heat-processing with a hot plate, hot air, oven, etc. Heating temperature is 80-140 degreeC normally, Preferably it is 90-120 degreeC. Heating time is 30-600 second normally, Preferably it is about 30-300 second.

The film thickness of the photosensitive resin film is not specifically limited, What is necessary is just to adjust suitably according to the pattern to be finally obtained. A film thickness is 0.5-10 micrometers normally, Preferably it is 1-5 micrometers. In addition, a film thickness can be adjusted with content of the solvent in the photosensitive resin composition, the application|coating method, etc.

・Exposure

Exposure is typically performed by shining an actinic ray on the photosensitive resin film through a suitable photomask.

Examples of the actinic rays include X-rays, electron beams, ultraviolet rays, visible rays, and the like. In terms of wavelength, light of 200 to 500 nm is preferable. It is preferable that a light source is g line|wire, h line|wire, or i line|wire of a mercury lamp from the point of the resolution and handling property of a pattern, and especially i line|wire is preferable. Moreover, you may mix and use two or more light rays. As the exposure apparatus, a contact aligner, mirror projection, or stepper is preferable.

What is necessary is just to adjust the light quantity of exposure suitably with the quantity of the photoinitiator in the photosensitive resin film, the film thickness of the photosensitive resin film, etc. The amount of light for exposure is, for example, about 100 to 500 mJ/cm ² .

After exposure, you may heat the photosensitive resin film again as needed (post-exposure heating: Post Exposure Bake). The heating temperature here is, for example, 70 to 150°C, preferably 90 to 120°C. The heating time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds. By heating after exposure, the polymerization reaction by the active species which generate|occur|produced from the photoinitiator is accelerated|stimulated, and the hardening reaction is accelerated|stimulated further. That is, further high sensitivity can be attained from a process point of view.

·phenomenon

By developing the exposed photosensitive resin film with a suitable developing solution, obtaining a pattern and the board|substrate provided with a pattern can be manufactured.

In a developing process, image development can be performed using methods, such as an immersion method, the puddle method, and the rotary spray method, using an appropriate developing solution, for example. By development, the exposed part (in the case of a positive type) or an unexposed part (in the case of a negative type) of the photosensitive resin film is eluted and removed, and a pattern is obtained. When the photosensitive resin composition of this embodiment is used, a negative pattern is normally obtained.

The developer that can be used is not particularly limited. For example, an aqueous alkali solution or an organic solvent can be used.

Specific examples of the aqueous alkali solution include (i) an inorganic aqueous alkali solution such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, (ii) an organic amine aqueous solution such as ethylamine, diethylamine, triethylamine, and triethanolamine, ( iii) aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide; and the like.

Specific examples of the organic solvent include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ether solvents such as propylene glycol monomethyl ether. and the like.

A developing solution may contain additives, such as water-soluble organic solvents, such as methanol and ethanol, and surfactant, for example.

In this embodiment, it is preferable to use an aqueous alkali solution as a developing solution, and it is more preferable to use the aqueous solution of tetramethylammonium hydroxide or sodium carbonate.

The density|concentration of aqueous alkali solution becomes like this. Preferably it is 0.1-10 mass %, More preferably, it is 0.5-5 mass %.

After image development, you may further perform various processes.

For example, after development, the pattern and/or the substrate may be washed with a rinse solution. As a rinse liquid, distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether etc. are mentioned, for example. These may be used independently and may be used in combination of 2 or more type.

Moreover, you may make it harden|harden enough by heating the obtained pattern. Heating temperature is 150-400 degreeC typically, Preferably it is 160-300 degreeC, More preferably, it is 200-250 degreeC. Although heating time is not specifically limited, For example, it exists in the range for 15 to 300 minutes. This heat treatment can be performed by a hot plate, an oven, a temperature rising type oven in which a temperature program can be set, or the like. As atmospheric gas at the time of heat processing, air may be sufficient and inert gas, such as nitrogen and argon, may be sufficient. Moreover, you may heat under reduced pressure.

According to the above process, the thing which obtains a pattern / the board|substrate provided with a pattern can be manufactured. More specifically, a color filter can be obtained using the photosensitive resin composition containing a coloring agent. Moreover, a black matrix can be obtained using the photosensitive resin composition containing a light-shielding agent. Furthermore, a display device (typically a liquid crystal display device) or an imaging device (typically a solid-state imaging device) including a color filter and/or a black matrix can be manufactured.

An example of the structure of a display device and/or an imaging element provided with a color filter and/or a black matrix is schematically shown in FIG.

On the substrate 10 , a black matrix 11 and a color filter 12 are formed. In addition, a protective film 13 and a transparent electrode layer 14 are provided on the black matrix 11 and the color filter 12 .

The board|substrate 10 is comprised by the material which passes light normally. For example, it is comprised by any one of glass, polyester, polycarbonate, polyolefin, polysulfone, the polymer of a cyclic olefin, etc.

The substrate 10 may have been subjected to corona discharge treatment, ozone treatment, chemical treatment, or the like.

The substrate 10 is made of, for example, glass.

The black matrix 11 is a hardened|cured material of the photosensitive resin composition containing a light-shielding agent normally.

As the color filter 12, three colors of red, green, and blue exist normally. The color filter 12 is a hardened|cured material of the photosensitive resin composition containing the coloring agent according to each color normally.

As mentioned above, although embodiment of this invention was described, these are illustrations of this invention, and various structures other than the above are employable. In addition, this invention is not limited to embodiment mentioned above, A deformation|transformation, improvement, etc. within the range which can achieve the objective of this invention are contained in this invention.

Example

EMBODIMENT OF THE INVENTION Embodiment of this invention is described in detail based on an Example and a comparative example. In addition, this invention is not limited to an Example.

About the compound used in an Example, it may represent with the following abbreviation|symbol or a brand name.

MA: maleic anhydride

NB: 2-norbornene

MEK: methyl ethyl ketone

BHEA: 2-hydroxyethyl acrylate

4-HBA: 4-hydroxybutyl acrylate

・A-TMM-3L: A mixture of the following two compounds, the amount of the compound on the left in the mixture based on gas chromatography measurement is about 55% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[Formula 21]

-A-TMM-3LM-N: A mixture of the following two compounds, the amount of the compound on the left in the mixture based on gas chromatography measurement is about 57% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[Formula 22]

・A-9550: A mixture of the following two compounds, the amount of the compound on the left in the mixture evaluated from the hydroxyl value is about 50% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[Formula 23]

<Synthesis of raw material polymer>

First, a raw material polymer containing a maleic anhydride structural unit and a 2-norbornene structural unit was synthesized. Details are shown below.

(Raw Polymer 1)

In an appropriately sized reaction vessel equipped with a stirrer and cooling tube, 353.02 g (3.6 mol) of maleic anhydride, 338.94 g (3.6 mol) of 2-norbornene, and dimethyl-2,2'-azobis (2- Methyl propionate) 33.16 g (0.144 mol) was weighed in. These were dissolved in a mixed solvent comprising 1030.1 g of methyl ethyl ketone and 113.0 g of toluene to prepare a solution.

This solution was vented with nitrogen for 30 minutes to remove oxygen, then heated at a temperature of 65° C. for 1.5 hours while stirring, and then heated again at 80° C. for 6 hours to obtain maleic anhydride and 2-norbornene. It was made to superpose|polymerize, and the polymerization solution was produced.

White solid was precipitated by dripping the polymerization solution obtained above to 8519.9 g of methanol. By vacuum-drying the obtained white solid at the temperature of 120 degreeC, 607.5 g of polymers (raw material polymer 1) provided with the structural unit derived from 2-norbornene and the structural unit derived from maleic anhydride were obtained.

As a result of measuring the obtained polymer using gel permeation chromatography (GPC), the weight average molecular weight Mw was 7000, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.82.

(Raw Polymer 2)

In an appropriately sized reaction vessel equipped with a stirrer and cooling tube, 353.02 g (3.6 mol) of maleic anhydride, 338.94 g (3.6 mol) of 2-norbornene, and dimethyl-2,2'-azobis (2- Methyl propionate) 33.16 g (0.144 mol) was weighed in. These were dissolved in the mixed solvent which consists of MEK2654.9g and toluene 113.0g, and the solution was produced.

This solution was vented with nitrogen for 30 minutes to remove oxygen, then heated with stirring at a temperature of 65°C for 1.5 hours, and then heated again at 80°C for 6 hours to polymerize maleic anhydride and 2-norbornene. and a polymerization solution was prepared.

White solid was reprecipitated by dripping the polymerization solution obtained above to methanol 13972.1g. By vacuum-drying the obtained white solid at the temperature of 120 degreeC, 569.1g of polymers (raw material polymer 2) provided with the structural unit derived from 2-norbornene and the structural unit derived from maleic anhydride were obtained.

As a result of GPC measurement of the obtained polymer, the weight average molecular weight Mw was 4300, and polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.59.

<Synthesis of polymer (ring-opening of structural unit derived from MA of raw material polymer)>

(Comparative Synthesis Example 1)

A polymer obtained by ring-opening the structural unit derived from MA of the raw material polymer 1 (hereinafter also simply referred to as "MA unit") with a hydroxyl group-containing trifunctional acrylate was prepared. Hereinafter, the detail is demonstrated.

First, 64.15 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, 96.85 g of A-TMM-3L (the amount to be added as a mixture of the above two types, hereinafter the same) was added to this solution, and then 9.00 g (0.089 mol) of triethylamine was added, and the temperature was 70°C. was reacted for 6 hours to prepare a reaction solution.

The aqueous phase was removed from the reaction solution by treating the prepared reaction solution with an aqueous formic acid solution. Thereafter, the polymer was purified by the following procedure.

· The polymer was reprecipitated with an excess of toluene.

- The operation of washing the polymer powder obtained by reprecipitation with an excess amount of toluene was repeated twice.

- Operation of washing the polymer powder after washing|cleaning the said 2 times with excess water was performed 3 times.

By the above, the polymer 23.39g which ring-opened the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3L was obtained.

(Comparative Synthesis Example 2)

A polymer in which the MA unit of the raw material polymer 1 was ring-opened only with a hydroxyl group-containing monofunctional acrylate was produced. Hereinafter, the detail is demonstrated.

First, 55.50 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, to this solution, 22.65 g (0.195 mol) of BHEA was added, and then, 9.00 g (0.089 mol) of triethylamine was added, and the reaction solution was made by reacting at 70°C for 6 hours. .

The aqueous phase was removed from the reaction solution by treating the obtained reaction solution with an aqueous formic acid solution. Then, the solution was poured into a large amount of pure water to precipitate a polymer. The obtained polymer was collected by filtration and washed again with pure water.

By the above, 27.21 g of polymers in which the structural unit derived from maleic anhydride in the raw material polymer was ring-opened only with BHEA was obtained.

(Comparative Synthesis Example 3)

A polymer in which the MA unit of the raw material polymer 1 was ring-opened only with a hydroxyl group-containing monofunctional acrylate was produced. Hereinafter, the detail is demonstrated.

First, 55.5 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Then, to this solution, 28.11 g (0.195 mol) of 4-HBA was added, then 9.00 g (0.089 mol) of triethylamine was added, and the reaction solution was reacted at 70°C for 6 hours. made

The aqueous phase was removed from the reaction solution by treating the obtained reaction solution with an aqueous formic acid solution. Then, the solution was poured into a large amount of pure water to precipitate a polymer. The obtained polymer was collected by filtration and washed again with pure water.

By the above, the polymer 26.54g which ring-opened the structural unit derived from maleic anhydride in the raw material polymer with 4-HBA was obtained.

(Synthesis Example 1)

A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was produced. Hereinafter, the detail is demonstrated.

First, 67.72 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, 58.12 g of A-TMM-3L was added with respect to this solution, and triethylamine 9.00 g (0.089 mol) was added after that, and it was made to react at the temperature of 70 degreeC for 2 hours. After that again, 22.65 g (0.195 mol) of BHEA was added, and the reaction solution was made to react at a temperature of 70°C for 4 hours.

The prepared reaction solution was purified in the same manner as in Comparative Synthesis Example 1 using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like.

As described above, 22.21 g of a polymer obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3L and BHEA was obtained.

(Synthesis Example 2)

A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was produced. Hereinafter, the detail is demonstrated.

First, 49.41 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, 19.37 g of A-TMM-3L was added to this solution, and then, 9.00 g (0.089 mol) of triethylamine was added thereto, and the mixture was reacted at a temperature of 70°C for 2 hours. After that again, 22.65 g (0.195 mol) of BHEA was added, and the reaction solution was made to react at a temperature of 70°C for 4 hours.

The prepared reaction solution was purified in the same manner as in Comparative Synthesis Example 1 using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like.

As described above, 22.53 g of a polymer obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3L and BHEA was obtained.

(Synthesis Example 3)

A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was produced. Hereinafter, the detail is demonstrated.

First, 49.51 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, 19.37 g of A-TMM-3L was added to this solution, and then, 18.00 g (0.178 mol) of triethylamine was added, and the reaction was carried out at a temperature of 70°C for 2 hours. After that again, 22.65 g (0.195 mol) of BHEA was added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

The prepared reaction solution was purified in the same manner as in Comparative Synthesis Example 1 using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like.

As described above, 22.10 g of a polymer obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3L and BHEA was obtained.

(Synthesis Example 4)

A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was produced. Hereinafter, the detail is demonstrated.

First, 49.86 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, 19.37 g of A-TMM-3L was added to this solution, and then, 9.00 g (0.089 mol) of triethylamine was added thereto, and the mixture was reacted at a temperature of 70°C for 2 hours. Then again, 28.13 g (0.195 mol) of 4-HBA was added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

The prepared reaction solution was purified in the same manner as in Comparative Synthesis Example 1 using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like.

As described above, 24.64 g of a polymer obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3L and 4-HBA was obtained.

(Synthesis Example 5)

A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was produced. Hereinafter, the detail is demonstrated.

First, 47.35 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, to this solution, 19.37 g of A-TMM-3L was added, and thereafter, 18.00 g (0.178 mol) of triethylamine was added, followed by reaction at a temperature of 70°C for 2 hours. Then again, 28.13 g (0.195 mol) of 4-HBA was added, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

The prepared reaction solution was purified in the same manner as in Comparative Synthesis Example 1 using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like.

By the above, 25.77 g of polymers obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3L and 4-HBA were obtained.

(Synthesis Example 6)

A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing pentafunctional acrylate and a hydroxyl group-containing monofunctional acrylate was prepared. Hereinafter, the detail is demonstrated.

First, 71.03 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, 43.78 g of A-9550 was added to this solution, and then, 9.00 g (0.089 mol) of triethylamine was added, and the mixture was reacted at a temperature of 70°C for 2 hours. Then, 22.65 g (0.195 mol) of BHEA was added to the reaction solution again after that, and it was made to react at the temperature of 70 degreeC for 4 hours, and the reaction solution was produced.

The prepared reaction solution was purified in the same manner as in Comparative Synthesis Example 1 using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like.

By the above, 25.51 g of polymers obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-9550 and BHEA were obtained.

(Synthesis Example 7)

A polymer in which the MA unit of the raw material polymer 2 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was prepared. Hereinafter, the detail is demonstrated.

First, 49.41 g of MEK was added to 30 g of the raw material polymer 2 (0.156 mol in terms of MA) to prepare a solution. Next, 19.37 g of A-TMM-3LM-N was added to this solution, and then, 9.00 g (0.089 mol) of triethylamine was added thereto, and the mixture was reacted at a temperature of 70°C for 2 hours. After that again, 22.65 g (0.195 mol) of BHEA was added, and the reaction solution was made to react at a temperature of 70°C for 4 hours.

The prepared reaction solution was purified in the same manner as in Comparative Synthesis Example 1 using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like.

By the above, 21.11 g of polymers obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3L and BHEA were obtained.

(Synthesis Example 8)

A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was produced. Hereinafter, the detail is demonstrated.

First, 50.60 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, 7.75 g of A-TMM-3LM-N was added to this solution, and then, 9.00 g (0.089 mol) of triethylamine was added thereto, and the mixture was reacted at a temperature of 70°C for 2 hours. After that again, 22.65 g (0.195 mol) of BHEA was added, and the reaction solution was made to react at a temperature of 70°C for 4 hours.

The prepared reaction solution was purified in the same manner as in Comparative Synthesis Example 1 using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like.

As described above, 20.66 g of a polymer obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3LM-N and BHEA was obtained.

(Synthesis Example 9)

A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was produced. Hereinafter, the detail is demonstrated.

First, 46.60 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, 7.75 g of A-TMM-3L was added to this solution, and 18.00 g (0.178 mol) of triethylamine was added after that, and it was made to react at the temperature of 70 degreeC for 2 hours. After that again, 22.65 g (0.195 mol) of BHEA was added, and the reaction solution was made to react at a temperature of 70°C for 4 hours.

The prepared reaction solution was purified in the same manner as in Comparative Synthesis Example 1 using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like.

By the above, the polymer 21.22g which ring-opened the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3L and BHEA was obtained.

(Synthesis Example 10)

A polymer in which the MA unit of the raw material polymer 1 was ring-opened with a hydroxyl group-containing trifunctional acrylate and a hydroxyl group-containing monofunctional acrylate was produced. Hereinafter, the detail is demonstrated.

First, 54.13 g of MEK was added to 30 g of the raw material polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, 29.06 g of A-TMM-3LM-N was added to this solution, and thereafter, 18.00 g (0.178 mol) of triethylamine was added, followed by reaction at a temperature of 70°C for 2 hours. After that again, 22.65 g (0.195 mol) of BHEA was added, and the reaction solution was made to react at a temperature of 70°C for 4 hours.

The prepared reaction solution was purified in the same manner as in Comparative Synthesis Example 1 using an aqueous formic acid solution, an excess amount of toluene, an excess amount of water, and the like.

As described above, 24.54 g of a polymer obtained by ring-opening the structural unit derived from maleic anhydride in the raw material polymer with A-TMM-3LM-N and BHEA was obtained.

<GPC measurement>

For each polymer, the weight average molecular weight and the degree of dispersion (weight average molecular weight/number average molecular weight) were determined by GPC measurement using polystyrene as a standard substance.

Moreover, disappearance of the peak of the acrylate compound (BHEA, 4-HBA, A-TMM-3L, A-TMM-3LM-N, A-9550) was confirmed by GPC measurement. That is, in the polymers of each synthesis example and comparative synthesis example, the MA unit and unreacted acrylate of the raw material polymer and the acrylate compound (acrylate not containing a hydroxyl group) that does not react with the original MA unit are sufficiently removed. confirmed that

<NMR measurement of polymer>

¹ H-NMR measurement was performed for the polymers of each synthesis example and comparative synthesis example.

^{Based on the integral value of the 4H peak (around 8.1 ppm) of the phenyl group of the standard dimethyl terephthalate in 1} H-NMR measurement, the integral value of the H peak (around 12.4 ppm) of the carboxyl group (-COOH) of the polymer The amount of carboxyl groups was obtained from And the acid value (mgKOH/g) was computed from the quantity.

It shows that there is much quantity of the carboxyl group per polymer unit mass, so that the value of an acid value is large.

Similarly, based on the integral value of the 4H peak (near 8.1 ppm) of the phenyl group of dimethyl terephthalate, _{the 3H peak of the acryloyl moiety (CH 2} =CH-COO-) in the polymer (near 6.2 ppm) The amount of C = C double bonds was calculated from the integral value of , and the double bond equivalent (mass of polymer per mole of C = C double bonds, g/mol) was calculated from the amount.

A smaller value of the double bond equivalent indicates a larger amount of C=C double bonds per unit mass of the polymer.

In Table 1, for the polymers of each Synthesis Example and Comparative Synthesis Example, the acrylate compound used in the synthesis, the weight average molecular weight of the polymer, the dispersion degree, the acid value, and the double bond equivalent are collectively shown.

In addition, the first structural unit of, R ^D is 2 or more polymerizable carbon-carbon double bond ratio of resulting structural unit containing a carbon-carbon double bond and, claim 1 of the structural unit, R ^D is a single polymerizable carbon Table 1 also shows the ratio (ratio in all the structural units of the polymer) of the structural units to be included. These ratios were obtained by solving the "simultaneous equations" as described above on the assumption that the ratio of the norbornene structural unit to the maleic anhydride structural unit in the raw material polymer 1 or 2 was 50:50 (molar ratio).

For the sake of brevity, in each polymer, the sum of these two ratios is less than 50 mol %. From this point, it can be said that all of the maleic anhydride structural units in a polymer are not ring-opening, but it is the state which is a structure represented by Formula (MA) in part.

[Table 1]

Here, from the numerical value of the acid value and double bond equivalent of the polymer of the Synthesis Example, in the polymers of Synthesis Examples 1 to 10, a structural unit represented by the general formula (1), and R ^D contains two or more polymerizable carbon-carbon double bonds It is supported that it contains a cause that does. This will be described below.

Consider ring-opening of the MA unit in the raw material polymer by a compound having a hydroxyl group and a polymerizable carbon-carbon double bond.

When a compound having one molecule of a hydroxyl group and a polymerizable carbon-carbon double bond opens the MA unit of 1, one carboxyl group is produced as shown in the general formula (1).

Here, when the compound having a hydroxyl group and a polymerizable carbon-carbon double bond is a monofunctional compound such as BHEA or 4-HBA, the number of C=C double bonds introduced is one. That is, one carboxyl group and one C=C double bond increase by one ring opening of one MA unit.

On the other hand, when the compound having a hydroxyl group and a polymerizable carbon-carbon double bond is a polyfunctional compound such as A-TMM-3L or A-9550, due to ring opening of one MA unit, one carboxyl group, C=C double bonds increase by "2 or more".

On the other hand, in the case of two or more polymers having the same acid value (that is, the degree of ring-opening of the MA unit being the same), the polymer in which the MA unit is ring-opened with the polyfunctional compound is higher than the polymer in which the MA unit is ring-opened with the monofunctional compound. , the double bond equivalent becomes smaller.

On this basis, check the above table.

The acid values of the polymers of Synthesis Examples 1 to 10 (corresponding to the amount of carboxyl group generated by ring opening) are about the same as or smaller than the acid values of the polymers of Comparative Synthesis Examples 2 and 3 (the ones in which the MA unit is ring-opened only with a monofunctional compound) . Nevertheless, the double bond equivalent of the polymers of Synthesis Examples 1 to 10 tends to be smaller than that of the polymers of Comparative Synthesis Examples 2 and 3 (that is, the amount of C=C double bonds per unit mass of the polymer is large). This indicates that a structure derived from a polyfunctional compound such as A-TMM-3L or A-9550 is introduced into the polymers of Synthesis Examples 1 to 10.

From the synthesis procedure, it is not clear that a structure derived from a polyfunctional compound such as A-TMM-3L or A-9550 is introduced into the raw material polymer. The introduction of structures derived from functional compounds is supported.

<Evaluation>

[Evaluation of developability] (dissolution rate of polymer in TMAH aqueous solution)

The polymer of each synthesis example and the comparative synthesis example was melt|dissolved in propylene glycol monomethyl ether acetate (PGMEA), and the solution of 30 mass % of solid content concentration was produced.

Next, the solution was spin-coated on the wafer, the PGMEA was dried, and prebaked at a temperature of 100°C for 2 minutes to prepare a resin film having a film thickness of about 2 µm.

This resin film was immersed in 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution at a temperature of 23 degreeC for every wafer, and the dissolution rate of the resin film was measured.

The dissolution rate was calculated by visually observing the immersed wafer, measuring the time until the resin film melted and the interference pattern was no longer seen, and dividing the film thickness from that time.

The goodness and badness of developability were judged by the following reference|standard.

○ (good): dissolution rate 500 nm/s or more

x (bad): dissolution rate less than 500 nm/s

[Sensitivity evaluation] (2.0 mass % sodium carbonate aqueous solution)

First, the photosensitive resin composition which melt|dissolved the following components in propylene glycol monomethyl ether acetate (PGMEA) was obtained so that total solid content concentration might be set to 30 mass %.

-Polymer (Synthesis Examples 1 to 10 or Comparative Synthesis Examples 1 to 3): 100 parts by mass

-Polyfunctional acrylate (dipentaerythritol hexaacrylate): 50 parts by mass

・Photoinitiator (manufactured by BASF, Ingacure OXE01): 5 parts by mass

· Adhesion aid (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403): 1 part by mass

・Surfactant (manufactured by DIC Corporation, F-556): 0.5 parts by mass

The obtained resin composition was spin-coated on a 3-inch silicon wafer treated with HMDS (Hexamethyldisilazane), and baked on a hot plate at 100°C for 120 seconds to obtain a thin film A having a thickness of about 3.0 µm (±0.3 µm).

In this thin film A, through a photomask having a gradation of 1 to 100% of light blocking rate, g+ with an exposure amount of 100 ^{mJ/cm 2 with a g+h+i line mask aligner (PLA-501F) manufactured by Canon Co., Ltd.} The h+i line was exposed.

After exposure, the thin film was developed with 2.0 mass % sodium carbonate aqueous solution at 23° C. for 60 seconds (immersed for each wafer) to obtain a thin film B exposed and developed at each exposure dose of ^{1 to 100 mJ/cm 2 .}

From the film thicknesses of the thin film A and the thin film B obtained by the said method, the remaining-film rate was computed from the following formula|equation.

Remaining film ratio (%) = (thickness of thin film B/thickness of thin film A at each exposure dose) x 100

And the following reference|standard evaluated the exposure amount used as 95 % or more of the remaining-film rate as a sensitivity of each photosensitive resin composition.

◎ (sensitivity is very good): 20 mJ/cm ² or less

○ (good sensitivity): 21-50 mJ/cm ²

× (poor sensitivity): 51 mJ/cm ² or more

[Evaluation of developability] (addition: rate of dissolution of polymer in _{Na 2} CO _{3 aqueous solution)}

In order to find the adaptability to various development processes, etc., the developability in the case of using sodium carbonate aqueous solution as a developing solution was also evaluated.

Specifically, with respect to a composition using any one of Synthesis Examples 1 to 10 as a polymer among the photosensitive resin compositions prepared in the above [Sensitivity evaluation], a 2.0 mass % sodium carbonate aqueous solution is used as a developer, and as a procedure, the above [development property evaluation], and the preparation of the resin film and the measurement of the dissolution rate were performed. And the following criteria evaluated.

○ (good): dissolution rate 50 nm/s or more

x (bad): dissolution rate less than 50 nm/s

An evaluation result is put together and shown below.

[Table 2]

As shown in Table 2, in the evaluation using the polymers of Synthesis Examples 1 to 10, both performance of developability and sensitivity were good. That is, it was possible to make the sensitivity and developability compatible.

In particular, about developability, not only the case where a TMAH developing solution was used, but also the case where sodium carbonate developing solution was used was favorable. It is understood that the photosensitive resin composition or polymer of this embodiment has favorable solubility with respect to various types of developing solutions.

On the other hand, in the evaluation using the polymer of Comparative Synthesis Example 1, developability was poor. Although a relatively large amount of polymerizable carbon-carbon double bonds were contained in the polymer (double bond equivalent: 286 g/mol), it is thought that sufficient developability was not obtained because the acid value was small, less than 70 mgKOH/g. .

Moreover, in the evaluation using the polymers of Comparative Synthesis Examples 2 and 3, the sensitivity was poor. It is thought that it is because the double bond of the density required for high sensitivity did not exist in the polymer.

<Production of color filter>

In the photosensitive resin composition prepared in [Sensitivity evaluation], to what contains the polymer of Synthesis Example 1, a pigment dispersion NX-061 (manufactured by Daiichi Seika Kogyo Co., Ltd., green) in an appropriate amount was added in an appropriate amount to prepare a colored photosensitive resin composition did. A green color filter was able to be formed by forming this into a film on a board|substrate, and performing exposure, alkali development, etc.

Moreover, as a pigment dispersion liquid, instead of NX-061, the blue or red color filter was able to be formed using NX-053 (blue), NX-032 (red), etc. manufactured by the same company.

Moreover, these color filters had sufficient resistance with respect to the high temperature which may be exposed in the device manufacturing process. It is thought that it is related to this that a polymer contains the structural unit which has a cyclic hydrocarbon skeleton.

<Production of the Black Matrix>

Among the photosensitive resin compositions prepared in [Sensitivity Evaluation], to those containing the polymer of Synthesis Example 1, a black photosensitive resin composition to which an appropriate amount of carbon black dispersion NX-595 (manufactured by Daiichi Seika Kogyo Co., Ltd.) was added was prepared. A black matrix was able to be formed by forming this into a film on a board|substrate, and performing exposure, alkali development, etc.

Moreover, this black matrix had sufficient tolerance with respect to the high temperature which can be exposed in a device manufacturing process. It is thought that it is related to this that a polymer contains the structural unit which has a cyclic hydrocarbon skeleton.

This application claims the priority on the basis of Japanese application Japanese Patent Application No. 2019-015715 for which it applied on January 31, 2019, and uses all the indication here.

Claims (23)

The photosensitive resin composition which has a 1st structural unit represented by the following general formula (1), is an acid value of 70-300 mgKOH/g, and contains the polymer whose double bond equivalent is 100-500 g/mol.

In General Formula (1), R ^D is a group containing a polymerizable carbon-carbon double bond. The method according to claim 1,
The photosensitive resin composition in which the said 1st structural unit contains the structural unit in which R ^D is a group containing two or more polymerizable carbon-carbon double bonds. The method according to claim 1 or 2,
wherein the first structural unit comprises a structural unit in which R ^D is a group containing two or more polymerizable carbon-carbon double bonds and a structural unit in which R ^D is a group containing only one polymerizable carbon-carbon double bond, A photosensitive resin composition. 4. The method according to any one of claims 1 to 3,
The photosensitive resin composition in which the said polymer further contains the 2nd structural unit represented by a following formula (MA).

5. The method according to any one of claims 1 to 4,
The photosensitive resin composition in which the said polymer further contains the structural unit which has a cyclic hydrocarbon skeleton. 6. The method according to any one of claims 1 to 5,
The photosensitive resin composition whose ratio of the said 1st structural unit in all the structural units of the said polymer is 10-40 mol%. 7. The method according to any one of claims 1 to 6,
The photosensitive resin composition whose weight average molecular weights of the said polymer are 6,000-25,000. 8. The method according to any one of claims 1 to 7,
A photosensitive resin composition further comprising a colorant. 8. The method according to any one of claims 1 to 7,
The photosensitive resin composition further comprising a light-shielding agent. A polymer having a first structural unit represented by the following general formula (1), an acid value of 70 to 300 mgKOH/g, and a double bond equivalent of 100 to 500 g/mol.

In General Formula (1), R ^D is a group containing a polymerizable carbon-carbon double bond. 11. The method of claim 10,
The first structural unit is ^{a polymer including a structural unit in which R D} is a group containing two or more polymerizable carbon-carbon double bonds. 12. The method of claim 10 or 11,
Wherein the first structural unit, R ^D is the polymerization of two or more carbon-polymer comprising a group structure unit containing a carbon-carbon double bond is a group structure comprising a carbon-carbon double bond units and, R ^D single polymerizable carbon . 13. The method according to any one of claims 10 to 12,
The polymer further containing the 2nd structural unit represented by the following formula (MA).

14. The method according to any one of claims 10 to 13,
A polymer further comprising a structural unit having a cyclic hydrocarbon skeleton. 15. The method according to any one of claims 10 to 14,
The polymer whose ratio of the said 1st structural unit in all the structural units is 10-40 mol%. 16. The method according to any one of claims 10 to 15,
A polymer having a weight average molecular weight of 6,000 to 25,000. The pattern obtained using the photosensitive resin composition in any one of Claims 1-7. The color filter obtained using the photosensitive resin composition of Claim 8. A display device comprising the color filter according to claim 18 . An imaging element provided with the color filter of Claim 18. The black matrix obtained using the photosensitive resin composition of Claim 9. A display device comprising the black matrix according to claim 21 . The imaging element provided with the black matrix of Claim 21.

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