TW202035486A - Photosensitive resin composition, polymer, pattern, color filter, black matrix, display device and image sensor - Google Patents

Abstract

The invention provides a photosensitive resin composition containing a polymer having a first structural unit represented by general formula (1), and having an acid value of 70 to 300 mg KOH/g and a double bond equivalent of 100 to 500 g/mol. In addition, the invention provides a polymer having a first structural unit represented by general formula (1), and having an acid value of 70 to 300 mg KOH/g and a double bond equivalent of 100 to 500 g/mol. In general formula (1), RD represents a group containing a polymeric carbon-carbon double bond.

Description

Photosensitive resin composition, polymer, pattern, color filter, black matrix, display device and imaging element

The present invention relates to photosensitive resin compositions, polymers, patterns, color filters, black matrices, display devices, and imaging elements.

Display devices (liquid crystal displays, etc.) or imaging elements (CCD, CMOS, etc.) usually have color filters or black matrixes. In many cases, a photosensitive resin composition is used in the formation of a color filter or a black matrix. Specifically, a photosensitive resin film is formed on a substrate from a photocurable photosensitive resin composition, and the film is exposed and developed to form a pattern such as a color filter or a black matrix on the substrate.

Patent Document 1 describes a curable polymer containing an acid group, a polymerizable unsaturated group, and a blocked isocyanate group in the molecule, the acid value is 20 to 300 mgKOH/g, and the unsaturated group equivalent is 100 to 4,000 g/ mol, and the equivalent weight of blocked isocyanate groups is 400-6,000 g/mol. Furthermore, it is described that a color filter is formed using this curable polymer.

Patent Document 2 describes that a binder resin having a weight average molecular weight of 1000 to 6000, an acid value of 80 to 200 mgKOH/g, and an ethylenically unsaturated bond equivalent of 500 or less is used to form a black matrix.

Patent Document 3 describes a photosensitive resin obtained by making an ethylenically unsaturated monomer containing an ethylenically unsaturated monomer having a formula weight of 70 to 120 without a carboxyl group and an ethylenically unsaturated monomer containing a carboxyl group. It is obtained by reacting 1 mol of the carboxyl group in the copolymer formed by bulk radical polymerization with the epoxy group in the 0.2-0.9 mol epoxy-containing ethylenically unsaturated monomer. In addition, a photosensitive composition containing the photosensitive resin is described. Furthermore, it is described that a color filter is formed using this photosensitive composition. Patent Document 3 describes that the acid value of the photosensitive resin is preferably 20 to 200 mgKOH/g. Moreover, it is stated that the double bond equivalent of the photosensitive resin is preferably 300 to 1,000.

Patent Document 4 describes a method of combining a carboxyl group-containing polymer represented by a specific general formula with (i) a compound having a group reactive with carboxylic acid and an ethylenically unsaturated group or (ii) having a compound reactive with carboxylic acid An alkali-soluble resin obtained by reacting a compound with a silicon-based functional group and a photosensitive resin composition containing the alkali-soluble resin. Furthermore, it is described that a color filter is formed using this photosensitive resin composition. Patent Document 4 describes that the acid value of the alkali-soluble resin is preferably 25-100 mgKOH/g, and the ethylenically unsaturated group equivalent is preferably 50-400.

[Patent Document 1] International Publication No. 2014/141731 [Patent Document 2] Japanese Patent Application Publication No. 2015-197619 [Patent Document 3] JP 2011-33951 A [Patent Document 4] JP 2007-264433 A

When a photosensitive resin composition is used, especially a negative photosensitive resin composition is used to form a pattern, the ease of photocuring (ie sensitivity) of the exposed portion and the ease of solubility of the unexposed portion in the developer (developing property) Often becomes a trade-off relationship. In particular, in recent years, it is necessary to have both high-level sensitivity and developability against the background of further complication and miniaturization of liquid crystal display devices and solid-state imaging elements.

The inventors of the present invention conducted studies this time with one of the objectives of providing a photosensitive resin composition having both sensitivity and developability.

As a result of intensive research conducted by the inventors, the invention provided below was completed.

According to the present invention, the following are provided.

通式（1）中，R^D 係含有聚合性碳-碳雙鍵之基團。 2. 如1.之感光性樹脂組成物，其中， 前述第一結構單元包含R^D 係含有2個以上的聚合性碳-碳雙鍵之基團之結構單元。 3. 如1.或2.之感光性樹脂組成物，其中， 前述第一結構單元包含：R^D 係含有2個以上的聚合性碳-碳雙鍵之基團之結構單元、和R^D 係僅含有1個聚合性碳-碳雙鍵之基團之結構單元。 4. 如1.～3.中任一項之感光性樹脂組成物，其中， 前述聚合物還包含由以下式（MA）表示之第二結構單元。

5. 如1.～4.中任一項之感光性樹脂組成物，其中， 前述聚合物還包含具有環狀烴骨架之結構單元。 6. 如1.～5.中任一項之感光性樹脂組成物，其中， 前述聚合物的總結構單元中的前述第一結構單元的比率係10～40mol%。 7. 如1.～6.中任一項之感光性樹脂組成物，其中， 前述聚合物的重均分子量係6,000～25,000。 8. 如1.～7.中任一項之感光性樹脂組成物，其還含有著色劑。 9. 如1.～7.中任一項之感光性樹脂組成物，其還含有遮光劑。 10. 一種聚合物，其具有由以下通式（1）表示之第一結構單元，酸值係70～300mgKOH/g，且雙鍵當量係100～500g/mol。

通式（1）中，R^D 係含有聚合性碳-碳雙鍵之基團。 11. 如10.之聚合物，其中， 前述第一結構單元包含R^D 係含有2個以上的聚合性碳-碳雙鍵之基團之結構單元。 12. 如10.或11.之聚合物，其中 前述第一結構單元包含：R^D 係含有2個以上的聚合性碳-碳雙鍵之基團之結構單元、和R^D 係僅含有1個聚合性碳-碳雙鍵之基團之結構單元。 13. 如10.～12.中任一項之感光性樹脂組成物，其還包含由以下式（MA）表示之第二結構單元。

14. 如10.～13.中任一項之聚合物，其還包含具有環狀烴骨架之結構單元。 15. 如10.～14.中任一項之聚合物，其中， 總結構單元中的前述第一結構單元的比率係10～40mol%。 16. 如10.～15.中任一項之聚合物，其重均分子量係6,000～25,000。 17. 一種圖案，其使用1.～7.中任一項之感光性樹脂組成物而得。 18. 一種濾色器，其使用8.之感光性樹脂組成物而得。 19. 一種顯示裝置，其具備18.之濾色器。 20. 一種成像元件，其具備18.之濾色器。 21. 一種黑矩陣，其使用9.之感光性樹脂組成物而得。 22. 一種顯示裝置，其具備21.之黑矩陣。 23. 一種成像元件，其具備21.之黑矩陣。1. A photosensitive resin composition containing 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 the general formula (1), R ^D is a group containing a polymerizable carbon-carbon double bond. 2. The photosensitive resin composition according to 1., wherein the first structural unit includes a structural unit having an R ^{D group} containing two or more polymerizable carbon-carbon double bonds. 3. The photosensitive resin composition of 1. or 2., wherein the aforementioned first structural unit includes: an R ^D- based structural unit of a group containing two or more polymerizable carbon-carbon double bonds, and an R ^D- based A structural unit containing only one polymerizable carbon-carbon double bond group. 4. The photosensitive resin composition according to any one of 1. to 3., wherein the polymer further includes a second structural unit represented by the following formula (MA).

5. The photosensitive resin composition according to any one of 1. to 4., wherein the polymer further includes a structural unit having a cyclic hydrocarbon skeleton. 6. The photosensitive resin composition according to any one of 1. to 5., wherein the ratio of the first structural unit in the total structural unit of the polymer is 10 to 40 mol%. 7. The photosensitive resin composition according to any one of 1. to 6., wherein the weight average molecular weight of the polymer is 6,000 to 25,000. 8. The photosensitive resin composition according to any one of 1. to 7. which further contains a colorant. 9. The photosensitive resin composition of any one of 1. to 7. which further contains a sunscreen. 10. A polymer having the first structural unit represented by the following general formula (1), the acid value is 70-300 mgKOH/g, and the 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. 11. The polymer according to 10., wherein the first structural unit includes a structural unit of an R ^{D group} containing two or more polymerizable carbon-carbon double bonds. 12. The polymer of 10. or 11., wherein the aforementioned first structural unit includes: ^Rd is a structural unit of a group containing more than two polymerizable carbon-carbon double bonds, and R ^D contains only one The structural unit of the group of polymerizable carbon-carbon double bond. 13. The photosensitive resin composition according to any one of 10. to 12., which further includes a second structural unit represented by the following formula (MA).

14. The polymer of any one of 10.-13., which further comprises a structural unit having a cyclic hydrocarbon skeleton. 15. The polymer of any one of 10.-14., wherein the ratio of the aforementioned first structural unit in the total structural unit is 10-40 mol%. 16. The polymer of any one of 10.-15. has a weight average molecular weight of 6,000-25,000. 17. A pattern obtained by using the photosensitive resin composition of any one of 1. to 7. 18. A color filter obtained by using the photosensitive resin composition of 8. 19. A display device with the color filter of 18. 20. An imaging element with the color filter of 18. 21. A black matrix obtained by using the photosensitive resin composition of 9. 22. A display device with a black matrix of 21. 23. An imaging element with a black matrix of 21.

According to the present invention, a photosensitive resin composition having both sensitivity and developability can be provided. In addition, it is possible to provide polymers suitable for the production of such photosensitive resin compositions.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In all the drawings, the same components are denoted by the same symbols, and their descriptions are appropriately omitted. In order to avoid complexity, when there are multiple identical constituent elements in the same schema, sometimes only one of the constituent elements is marked with a symbol instead of all constituent elements. The diagram is for illustration only. The shape or size ratio of each part in the drawing does not necessarily correspond to the real article.

In this specification, the "double bond" of the "double bond equivalent" means a polymerizable carbon-carbon double bond. In this specification, unless otherwise specified, the term "approximately" means that a range that takes into account manufacturing tolerances or assembly deviations, etc. is included. In this specification, unless otherwise specified, the symbols "a to b" in the description of the numerical range indicate a or more and b or less. For example, "1 to 5 mass%" means "1 mass% or more and 5 mass% or less".

In the label of the group (atomic group) in the present specification, there is no description that the substituted or unsubstituted label includes both a group having no substituent and a group having a substituent. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl), but also substituted alkyl (substituted alkyl). The notation of "(meth)acrylic acid" in this specification means a concept including both acrylic acid and methacrylic acid. The same applies to similar marks such as "(meth)acrylate". Unless otherwise specified, the term "organic group" in this specification refers to an atomic group obtained by removing one or more hydrogen atoms from an organic compound. For example, the "monovalent organic group" refers to an atomic group obtained by removing one hydrogen atom from any organic compound.

<Photosensitive resin composition> The photosensitive resin composition of the present embodiment contains 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 The bond equivalent is 100～500g/mol. In the general formula (1), R ^D is a group containing a polymerizable carbon-carbon double bond.

By producing a photosensitive resin composition using the above-mentioned polymer, a photosensitive resin composition having both sensitivity and developability can be obtained. The reason can be explained as follows. In addition, the present invention should not be interpreted as being limited by the following description.

The structural unit represented by the general formula (1) includes "both" of a polymerizable carbon-carbon double bond-containing group (R ^D in the general formula) and a carboxyl group in one structural unit. The polymerizable group and the carboxyl group are in the same structural unit, so it is easy to design the "both" of the polymerizable group and the carboxyl group to a large value (think (meth)acrylic resin, etc.) This kind of design is difficult in resin). This case is advantageous in terms of improving the sensitivity and also improving the developability.

In addition, as the entire polymer, the acid value is designed to be 70 to 300 mgKOH/g, and the double bond equivalent is designed to be 100 to 500 g/mol, thereby achieving both high-level sensitivity and developability. That is, the acid value of the polymer is 70 mgKOH/g or more, whereby good developability can be obtained. In addition, the double bond equivalent is 500 g/mol or less, which can improve the sensitivity of the composition.

In addition, if the acid value is too large, when developing with an alkali developer, the exposed portion is easily dissolved, which may increase the amount of exposure required for photohardening, or the pattern shape may become insufficient. Therefore, in this embodiment, the upper limit of the acid value is set to 300 mgKOH/g. In addition, if the double bond equivalent is too small (that is, the density of the double bonds in the polymer is too large), the unexposed or low-exposure part tends to become difficult to dissolve during development with an alkali developer, and this tends to occur during development. Will produce residual film. In addition, if the double bond equivalent is too small, the molecular weight may increase excessively due to crosslinking, and the solubility may decrease excessively. Therefore, in this embodiment, the lower limit of the double bond equivalent is set to 100 g/mol.

The acid value of the polymer is 70 to 300 mgKOH/g, preferably 80 to 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 the polymer, a higher level of sensitivity and developability can be achieved.

It should be noted that the acid value and the double bond equivalent can be determined by spectrometry or the like. For example, it can be obtained by the following steps (for more specific description, please refer to the examples). (1) The area (integrated value) of the peak corresponding to the hydrogen atom of the carboxyl group or the hydrogen atom near the polymerizable carbon-carbon double bond is obtained from the ¹ H-NMR chart of the polymer. (2) Based on the area obtained in (1), the amount of carboxyl groups and the amount of carbon-carbon double bonds are obtained from the area of the peak derived from the standard material. (3) Convert the amount of carboxyl groups calculated in (2) into acid value (mgKOH/g). In addition, the amount of polymerizable carbon-carbon double bonds determined in (2) is converted into double bond equivalent (g/mol).

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

The components etc. which can be contained in the photosensitive resin composition of this embodiment are demonstrated below.

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

• The first structural unit The first structural unit preferably includes an R ^D- based structural unit containing two or more polymerizable carbon-carbon double bonds. In other words, a part or all of R ^{D in} 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, and still more preferably 3- 5. By adjusting the number of polymerizable double bonds contained in R ^D , a higher level of sensitivity and developability can be achieved.

When R ^D contains two or more polymerizable carbon-carbon double bonds, it is preferable that at least one (more preferably all) of the two or more polymerizable double bonds is present at the terminal of R ^D. With this structure, the polymerizable double bond easily reacts with the active chemical species generated from the photopolymerization initiator. Therefore, the sensitivity can be further improved.

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, R ^D contains 2 to 6, preferably 2 to 5, more preferably 3 to 5 (meth)acryloyl groups. In addition, in order to further improve the sensitivity, a (meth)acryl-based acrylic group is preferred. The reason is that, compared with the methacryloyl group, the unmethyl-substituted acrylic group is more likely to react with the active chemical species generated from the photopolymerization initiator.

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

In the general formula (1b), K is 2 or 3, R is a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different. X ¹ is a single bond, an alkylene group with 1 to 6 carbon atoms, or -ZX- represents a group of (Z is -O- or -OCO-, X is an alkylene group having a carbon number of 1 to 6), presence of a plurality of X ¹ may be also the same or different, X ¹ 'is a single bond, a carbon number of 1 ~6 alkylene group or a group represented by -X'-Z'- (X' is an alkylene group with 1 to 6 carbons, Z'is -O- or -COO-), X ² is a carbon number 1-12 k+1 valent organic group.

From the viewpoint of further improving sensitivity (easy degree of polymerization), etc., R-based hydrogen atoms are preferred. k may be 2 or 3, but from the viewpoint of the availability of raw materials or the further improvement of sensitivity, 3 is preferable.

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 carbons, X ^{1 is} preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbons, and still more preferably -CH ₂ -(Methylene).

When X ¹ is a group represented by -ZX- (Z is -O- or -OCO-, X is an alkylene having 1 to 6 carbons), the alkylene having 1 to 6 carbons of X may be The linear shape may also be branched. The alkylene having 1 to 6 carbon atoms of X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and still more preferably -CH ₂ -CH ₂ -(extension Ethyl) or -CH ₂ -CH(CH ₃ )-.

When X ¹ ′ is an alkylene group having 1 to 6 carbon atoms, the specific aspect is the same as X ¹ . When X ¹ 'is a group represented by -X'-Z'-, the specific aspect of X'is the same as the above-mentioned X.

Examples of the k+1 valent organic group having 1 to 12 carbons for X ² include any group obtained by removing k+1 hydrogen atoms from any organic compound. Among them, the "arbitrary organic compound" 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 carbons (preferably 1 to 6 carbons). More preferably, it is a group obtained by removing k+1 hydrogen atoms from a linear hydrocarbon having 1 to 3 carbon atoms. In addition, the hydrocarbon may contain oxygen atoms (such as ether bonds or hydroxyl groups). In addition, hydrocarbon-based saturated hydrocarbons are preferred. As another aspect, X ² may be a group containing a cyclic structure. As a group containing a cyclic structure, a group containing an alicyclic structure, a group containing a heterocyclic structure (for example, an isocyanuric acid structure), etc. can be mentioned.

In the general formula (1c), the definitions of k, R, X ¹ and X ² are the same as the definitions of R, k, X ¹ and X ² in the general formula (1b). A plurality of Rs may be the same or different from each other. X ¹ may be the same or different from each other, X ³ is a divalent organic group with 1 to 6 carbons, X ⁴ and X ⁵ are each independently a single bond or a divalent organic group with 1 to 6 carbons, and X ⁶ is a carbon A divalent organic group of 1 to 6.

The specific aspects and preferred aspects of R, k, X ¹ and X ² are the same as those explained by the general formula (1b). Examples of the divalent organic group having 1 to 6 carbons for X ³ and X ⁶ include groups obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to 6 carbons. In addition, the hydrocarbon may contain oxygen atoms (such as ether bonds or hydroxyl groups). In addition, hydrocarbon-based saturated hydrocarbons are preferred. Examples of the divalent organic group having 1 to 6 carbon atoms of X ⁴ and X ⁵ include linear or branched alkylene groups. The carbon number of the linear or branched alkylene group is preferably 1-3.

R ^D comprises structural units of the first system containing two or more polymerizable carbon - based structural units and R ^D to carbon double bond group containing only one polymerizable carbon - a group of the structural unit is preferably a carbon double bond . In another way, it is preferable that among the structural units represented by the general formula (1) in the polymer, R ^D in a part of the structural units is a group containing two or more polymerizable carbon-carbon double bonds. Among the structural units represented by the general formula (1), the R ^D in the remaining structural units contains only one polymerizable carbon-carbon double bond. By designing the polymer in this way, it is easy to obtain better developability while improving the sensitivity.

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

In "R ^D is a structural unit of a group containing only one polymerizable carbon-carbon double bond", the polymerizable double bond is preferably present at the terminal of R ^D. In addition, as one aspect, R ^D contains one (meth)acryloyl group. From the viewpoint of further improving the sensitivity, a (meth)acryloyl-based acryloyl group is preferred. More specifically, R ^D can be a group represented by the following general formula (2a).

In the general formula (2a), X ¹⁰ is a divalent organic group, and R is a hydrogen atom or a methyl group. The total carbon number of X ¹⁰ is preferably 1-30, more preferably 1-20, and still more preferably 1-10.

As the divalent organic group of X ¹⁰ , for example, an alkylene group is preferable. A part of -CH ₂ -in the alkylene group may be an ether group (-O-). The alkylene group may be straight-chain or branched, and straight-chain is more preferred.

The divalent organic group as X ¹⁰ is more preferably a linear alkylene group having 3 to 6 total carbons. By appropriately selecting the number of carbon X ¹⁰ (corresponding to the "length" X ^10), the group represented by the formula (2a) involved in the curing reaction more easily. Therefore, the sensitivity can be further improved.

The divalent organic group (for example, alkylene) of X ¹⁰ may be substituted with any substituent. As a substituent, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, etc. can be mentioned. In addition, the divalent organic group of X ¹⁰ may be any group other than an alkylene group. For example, it may be a divalent group constituted by linking one or more groups selected from alkylene, cycloalkylene, arylene, ether, carbonyl, carboxyl, and the like.

The ratio of the first structural unit in the total structural unit of the polymer is preferably 10-40 mol%, more preferably 15-35 mol%. Also, when the polymer comprises R ^D system containing two or more polymerizable carbon - based structural units and R ^D to carbon double bond group containing only one polymerizable carbon - a structural unit of a group of two carbon double bond When the former is used as the first structural unit, the molar ratio of the former: the latter is preferably 5:95-50:50, and more preferably 10:90-40:60. By appropriately adjusting the ratio, it is easy to achieve both higher sensitivity and developability. Here, the molar ratio of the former:the latter can be obtained as follows, for example. Set the amount of the former in the polymer as X ₁ (mol/g), the amount of the latter as X ₂ (mol/g), the amount of carboxyl groups as C (mol/g), polymerizable carbon-carbon double bond The amount of is set to D (mol/g). Furthermore, it is assumed that the former contains n polymerizable carbon-carbon double bonds. Both the former and the latter have 1 carboxyl group. Therefore, it is described as X ₁ +X ₂ =C (assuming that the polymer does not contain other structural units containing carboxyl groups). In addition, the amount of polymerizable carbon-carbon double bonds is described as n•X ₁ +X ₂ =D (assuming that the polymer does not contain other structural units containing polymerizable double bonds). C and D can be known from the peak area obtained from NMR measurement. In addition, n is determined based on the chemical structure of the raw material. Therefore, by using these two numerical formulas as simultaneous equations to find the unknowns X ₁ and X ₂ , the molar ratio of the former:the latter can be found. Further, it is possible with the X ₁ and X, ₂ of the base polymer (described later) of the number of moles of each structural unit contained in the (mol / g), the basis for the respective structural units contained in the polymer material of a single The ratio of the first structural unit (when there are a plurality of first structural units, the total) in the total structural units of the polymer is determined by the molecular weight of the polymer.

•The second structural unit Preferably, the polymer further includes a second structural unit represented by the following formula (MA). The second structural unit can be ring-opened by an alkaline developer. If the ring is opened, two carboxyl groups are generated, so it is considered that the developability can be further improved.

When the polymer contains the structural unit represented by the formula (MA), the ratio of the structural unit represented by the formula (MA) in the total structural unit of the polymer is preferably 1-25 mol%, more preferably 3-20 mol%.

• The solubility adjusting structural unit polymer may contain 1 or 2 or more structural units represented by the following general formula (a2-1), (a2-2) or (a2-3). By including such a structural unit in the polymer, it is possible to adjust the solubility to the developer, and to adjust the solubility to the organic solvent. In general formula (a2-1) and general formula (a2-2), R ₁₄ , R ₁₅ and R ₁₆ are each independently an organic group having 1 to 30 carbon atoms.

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. And, constituting R _14, R ₁₅ R ₁₆ and an organic group capable of containing an acidic functional group to those not. In this way, the acid value can be easily controlled.

Examples of the organic groups constituting R ₁₄ , R ₁₅ and R ₁₆ include alkyl groups, alkenyl groups, alkynyl groups, alkylene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, and heterocyclic groups. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, pentyl, neopentyl, hexyl, and heptyl. Base, octyl, nonyl, decyl, etc. Examples of alkenyl groups include allyl groups, pentenyl groups, and vinyl groups. As an alkynyl group, an ethynyl group etc. are mentioned, for example. As a ethylene group, a methine group, a ethylene group, etc. are mentioned, for example. As an aryl group, a phenyl group, a naphthyl group, an anthryl 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. As a cycloalkyl group, an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, etc. are mentioned, for example. As a heterocyclic group, an epoxy group, an oxetanyl group, etc. are mentioned, for example.

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

• Structural unit with cyclic hydrocarbon skeleton The polymer preferably contains a structural unit having a cyclic hydrocarbon skeleton. The rigid structure of the cyclic hydrocarbon skeleton can improve the heat resistance and mechanical properties of the cured film when the photosensitive resin composition is cured, for example.

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

Cyclic olefin monomers. Specifically, norbornene, norbornadiene, bicyclo[2.2.1]-hept-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl 2-Norcamene, 5-Butyl-2-Norbornene, 5-hexyl-2-Norbornene, 5-Decyl-2-Norbornene, 5-Allyl-2-Norbornene Alkene, 5-(2-propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethylidene-2-norbornene, Monomers such as 5-benzyl-2-norbornene and 5-phenethyl-2-norbornene, which have a norbornene skeleton or norbornadiene skeleton.

Indene, 2-methylindene, 3-methylindene, acenaphthylene and other monomers having an indene skeleton or acenaphthene skeleton. 11,5,9-cyclododecanetriene, cis-trans-trans-1,5,9-cyclododecanetriene, trans-trans-trans-1,5,9-cyclododecanetriene , Trans-cis-cis-1,5,9-cyclododecanetriene, cis-cis-cis-1,5,9-cyclododecanetriene and other monomers with triene structure. Styrene, vinyl toluene, hydroxystyrene, acetoxystyrene, α-methylstyrene and other monomers with styrene skeleton.

N-cyclohexyl maleimide, N-cyclopentyl maleimide, N-norbornyl maleimide, N-cyclohexyl methyl maleimide N-cycloalkyl maleimines such as amines and N-cyclopentylmethyl maleimines. N-phenylmaleimide, N-chlorophenyl maleimide, N-methylphenyl maleimide, N-naphthyl maleimide , N-hydroxyphenyl maleimide, N-methoxyphenyl maleimide, N-carboxyphenyl maleimide, N-nitrophenyl maleimide N-aryl maleimines such as enediimines.

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 a norbornadiene skeleton is more preferable. More specifically, the structural unit having a cyclic hydrocarbon skeleton is preferably represented by the following general formula (NB).

In 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, and a ₁ is 0, ₁ , or 2.

Examples of the organic groups having 1 to 30 carbon atoms in R ¹ , R ² , R ³ and R ⁴ in the general formula (NB) include alkyl groups, alkenyl groups, alkynyl groups, alkylene groups, aryl groups, and aralkyl groups. Group, alkaryl group, cycloalkyl group, alkoxy group, heterocyclic group, carboxyl group, etc.

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, pentyl, neopentyl, hexyl, and heptyl. Base, octyl, nonyl, decyl, etc. Examples of alkenyl groups include allyl groups, pentenyl groups, and vinyl groups. As an alkynyl group, an ethynyl group etc. are mentioned, for example. As a ethylene group, a methine group, a ethylene group, etc. are mentioned, for example. Examples of aryl groups include tolyl, xylyl, phenyl, naphthyl, and anthracenyl. 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. As a cycloalkyl group, an adamantyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group etc. are mentioned, for example. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second butoxy, isobutoxy, tertiary butoxy, n Pentyloxy, neopentyloxy, n-hexyloxy, etc. 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 preferred, and hydrogen is more preferred. The hydrogen atom in the C 1-30 organic group of R ¹ , R ² , R ³ and R ⁴ may be substituted with any atomic group. For example, it may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, and the like. More specifically, as the C 1-30 organic group of R ¹ , R ² , R ³ and R ⁴ , a fluorinated alkyl group or the like can 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% in the total structural units of the polymer, more preferably 30 to 70 mol%, and still more preferably 40 to 60 mol%. By appropriately adjusting the ratio, it is easy to obtain additional effects (for example, improvement of heat resistance or improvement of mechanical properties when used as a cured film) while having both sensitivity and developability. Incidentally, from the viewpoint of overall performance or cost, the polymer does not contain any difference from the first structural unit as an essential structural unit, the second structural unit as an arbitrary structural unit, and the structural unit having a cyclic hydrocarbon skeleton. "Other structural units", or a small amount even if it is contained, is preferable. Specifically, the ratio of the "other structural unit" in the polymer is preferably 0-20 mol%, more preferably 0-10 mol%.

The weight average molecular weight of the polymer is preferably from 6,000 to 25,000, more preferably from 7,000 to 20,000. By appropriately adjusting the weight average molecular weight, it is possible to appropriately adjust the solubility to the alkali developer, the solubility to the organic solvent, and the like. The degree of dispersion of the polymer (weight average molecular weight Mw/number average molecular weight Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and still more preferably 1.0 to 3.0. By appropriately adjusting the degree of dispersion, the physical properties of the polymer can be made uniform, which is preferable. These values can be obtained by gel permeation chromatography (GPC) measurement using polystyrene as a standard.

The polymer can be produced (synthesized) by any method. For example, a polymer can be produced by the following steps, namely • The preparation step is to prepare a raw polymer containing at least the structural unit represented by the aforementioned formula (MA); and • In the reaction step, in the presence of a basic catalyst, the raw material polymer is reacted with a compound having a hydroxyl group and a polymerizable carbon-carbon double bond.

Hereinafter, the method of producing (synthesizing) a polymer through the above-mentioned preparation step and reaction step will be further specifically described. In the description, the synthesis of a polymer including the structural unit represented by the general formula (1) and the structural unit represented by the general formula (NB) is taken as an example, but the generality of the polymer manufacturing method will not be lost. For example, a polymer containing a structural unit represented by the general formula (1) and a structural unit (copolymerization unit) not represented by the general formula (NB) can also be synthesized by a procedure similar to the following description.

•Preparation step The base polymer can be obtained, for example, by polymerizing (addition polymerization) 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). The preferred aspect is also the same.

As the monomer represented by the general formula (NB-m), for example, bicyclo[2.2.1]-hept-2-ene (common name: 2-norbornene), 5-methyl-2-nor Camphene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl 2-norcamphetene, 5-(2-propenyl)-2-norcampoene, 5-(1-methyl-4-pentenyl)-2-norcampoene, 5-ethynyl-2 -Norbornene, 5-benzyl-2-norbornene, 5-phenylethyl-2-norbornene, 2-acetyl-5-norbornene, 5-norbornene-2-carboxylic acid Methyl ester, 5-norbornene-2,3 dicarboxylic acid anhydride, norbornadiene, etc. During the polymerization, the monomer represented by the general formula (NB-m) may be used alone or in combination of two or more.

The method of polymerization is not limited, but radical polymerization using a radical polymerization initiator is preferred. As the polymerization initiator, for example, an azo compound, an organic peroxide, etc. can be used. As the azo compound, specifically, azobisisobutyronitrile (AIBN), 2,2'-azobis(2-methylpropionic acid) dimethyl ester, 1,1'-azobis (Cyclohexanecarbonitrile) (ABCN) and so on. Examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (BPO), methyl ethyl ketone peroxide (MEKP), and the like. Regarding the polymerization initiator, only one type may be used, or two or more types may be used in combination.

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

The monomer represented by the general formula (NB-m), the maleic anhydride, and the polymerization initiator are dissolved in a solvent and then placed in a reaction vessel, and then heated to perform addition polymerization. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 5 to 20 hours. The molar ratio of the monomer represented by the general formula (NB-m) to the maleic anhydride when it is charged into the reaction vessel is preferably 0.5:1 to 1:0.5. From the viewpoint of controlling the molecular structure, a molar ratio of 1:1 is preferred. The "raw polymer" can be obtained through the above steps. In addition, the base polymer may be any of random copolymers, alternating copolymers, block copolymers, periodic copolymers, and the like. It is typically a random copolymer or an alternating copolymer (usually, maleic anhydride is known as a monomer with strong alternating copolymerization).

After the raw polymer is synthesized, a step of removing low molecular weight components such as unreacted monomers, oligomers, and remaining polymerization initiators can be performed. Specifically, the organic layer containing the synthesized raw material polymer and low molecular weight components is concentrated, and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. Next, this solution is mixed with a poor solvent such as methanol to precipitate the monomer. The purity of the raw material polymer can be improved by filtering and drying the sediment.

• Reaction steps In the presence of a basic catalyst, the base polymer obtained in the preparation step is reacted with a compound having a hydroxyl group and a polymerizable carbon-carbon double bond, thereby the structural unit of formula (MA) contained in the base polymer Open loop. Thereby, the structural unit of general formula (1) is formed.

More specifically, first, a polymer solution obtained by dissolving a base polymer in an appropriate organic solvent is prepared. Examples of organic solvents that can be used here include methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAC), and N-methylpyrrolidone ( Single solvent or mixed solvent such as NMP) and tetrahydrofuran (THF). Of course, the solvent is not limited to these, and various organic solvents used in the synthesis of organic compounds or polymers can be used.

Next, a compound having a hydroxyl group and a polymerizable carbon-carbon double bond is added to the polymer solution. Furthermore, an alkaline catalyst is added. Furthermore, they are mixed appropriately to form a uniform solution.

As the compound having a hydroxyl group and a polymerizable carbon-carbon double bond, for example, a compound containing 1 or 2 or more (meth)acryloyl groups and a hydroxyl group can be cited. By using a compound (polyfunctional compound) containing two or more (meth)acrylic groups and hydroxyl groups, it can be introduced into the polymer. In the general formula (1), the R ^D system contains two or more polymerizable carbons- The structural unit of the carbon double bond group. On the other hand, by using a compound (monofunctional compound) containing only one (meth)acryloyl group and a hydroxyl group, it can be introduced into the polymer. In the general formula (1), the R ^D system contains only one polymerizable The structural unit of the group of carbon-carbon double bond. By using both of these polyfunctional compounds and monofunctional compounds, it is possible to convert the R ^D system to a structural unit containing two or more polymerizable carbon-carbon double bonds and the R ^D system to contain only one polymerizable carbon -The two structural units of the carbon double bond group are introduced into the polymer as the first structural unit. Among them, from the perspective of steric hindrance, monofunctional compounds have a tendency to react with polymers more easily than polyfunctional compounds. Therefore, in the reaction step, the monofunctional compound is not charged into the reaction system from the beginning to perform "addition". For better.

As a "compound containing two or more (meth)acrylic groups and a hydroxyl group", specifically, a compound represented by the following general formula (1b-m) or a compound represented by the following general formula (1c-m) can be cited The compound. 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 those 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 those of the general formula (1c).

As a compound containing two or more (meth)acrylic groups and a hydroxyl group, the following shows that it can be used suitably. In addition, it is also possible to use a part or all of the acryloyl groups of the compounds shown below as (meth)acryloyl groups (or the opposite).

On the other hand, as "compounds containing only one (meth)acryloyl group and a hydroxyl group", for example, compounds represented by the following general formula (2a-m) can be cited. In the general formula (2a-m), the definitions and specific aspects of X ¹⁰ and R are the same as those in the general formula (2a).

Specific examples of the compound represented by the general formula (2a-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 1,4-cyclohexanedimethanol Mono(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl -(meth)acrylate, 2- (Methyl) propylene oxyethyl-2-hydroxyethyl phthalic acid, etc.

After the reaction step, the reaction solution is diluted with an organic solvent, and/or an acid is added to neutralize the alkaline catalyst, thereby stopping the reaction. The polymer can be obtained through the above steps.

For reference only, in the reaction step, by appropriately adjusting the amount of the compound having a hydroxyl group and a polymerizable carbon-carbon double bond, etc., the maleic anhydride structure in the raw polymer will not be completely ring-opened and the final polymer Will contain the structure of formula (MA). In addition, in the reaction step, the maleic anhydride structure in the base polymer can be reacted with water, alcohol, and other appropriate substances to convert the formula (a2-1), (a2-2) or (a2- 3) The indicated structural unit is introduced into the polymer.

In order to remove unnecessary components and the like other than the desired polymer, it is further preferable to appropriately perform the following steps.

First, use a separatory funnel to dilute the above-mentioned organic solvent and add acid (such as formic acid, etc.) to the reaction solution and vigorously stir for at least 3 minutes. Let it stand for more than 30 minutes to separate into an organic phase and an aqueous phase, and remove the aqueous phase. In this way, an organic solution of the polymer is obtained.

An excess of toluene was added to the organic solution of the obtained polymer to re-precipitate the polymer. Furthermore, the polymer powder obtained by reprecipitation was washed several times with toluene. Furthermore, in order to remove formic acid or alkaline catalyst, the operation of washing the obtained polymer powder with ion exchange water was repeated several times (about 3 times). The polymer powder after washing with ion-exchange water is dried, for example, at 30 to 60°C for 16 hours or more, whereby a high-purity polymer can be obtained.

(Photopolymerization initiator) The photosensitive resin composition of this embodiment preferably contains a photopolymerization initiator. As long as the component generated by light irradiation reacts the polymerizable double bond contained in the structural unit of the general formula (1) of the polymer, any one can be used as a photopolymerization initiator. The photopolymerization initiator may be, for example, a photoradical polymerization initiator, a photocationic polymerization initiator, a photoanionic polymerization initiator, and the like. In addition, the photopolymerization initiator typically generates active chemical species by irradiation with ultraviolet light, more specifically, g-ray, i-ray, or the like.

From the viewpoint of higher sensitivity, the photopolymerization initiator is preferably a photoradical polymerization initiator. The radical photopolymerization initiator is not particularly limited, and a known compound can be suitably used. For example, the following compounds can be mentioned.

啉基丙烷1-酮、2-苄基-2-二甲胺基-1-（4-

啉基苯基）-丁酮-1、2-二甲胺基-2-〔（4-甲基苯基）甲基〕-1-〔4-（4-

啉基）苯基〕-1-丁酮等烷基苯酮系化合物。2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-benzene Propane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4- [4-(2-Hydroxy-2-methylpropanyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-(4-methylphenylthio)- 2-

Linyl propane 1-ketone, 2-benzyl-2-dimethylamino-1-(4-

Alkylphenyl)-butanone-1, 2-dimethylamino-2-[(4-methylphenyl)methyl]-1-[4-(4-

Alkylphenone-based compounds such as linyl)phenyl]-1-butanone.

Benzophenone compounds such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 2-carboxybenzophenone. Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin compounds. Thioxanthone (thioxanthone), 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone compounds such as xanthone.

2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-symmetric tris, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl) )-Symmetric tris, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-symmetric tris, 2-(4-ethoxycarbonylnaphthyl)-4,6 -Bis(trichloromethyl)-symmetrical tris, and other halomethylated tris series compounds. 2-Trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-〔β-(2'-benzofuranyl) Vinyl]-1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and other halomethylated oxadiazole series Compound.

2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorobenzene Yl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5 , 5'-tetraphenyl-1,2'-biimidazole and other biimidazole compounds. 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzyloxime)], O-acetyl-1-[6-(2-methylbenzyl (Acidyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime and other oxime ester compounds. Titanocene compounds such as bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium. Benzoate compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid. Acridine compounds such as 9-phenylacridine.

The photosensitive resin composition may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators. The amount of the photopolymerization initiator used is, for example, 1-20 parts by mass, preferably 3-10 parts by mass with respect to 100 parts by mass of the polymer.

(Solvent) The photosensitive resin composition of this embodiment typically contains a solvent. Thereby, a uniform photosensitive resin film can be formed on the surface of various substrates. As the solvent, an organic solvent can be preferably used. Specifically, one or two or more of ketone solvents, ester solvents, ether solvents, alcohol solvents, lactone solvents, carbonate solvents, and the like can be used.

Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), γ-butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl n-pentanone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone or A mixture of these.

The amount of solvent used is not particularly limited. For example, it is used in an amount such that the concentration of the non-volatile component becomes 10 to 70% by mass, preferably 15 to 60% by mass.

(Crosslinking agent) The photosensitive resin composition of this embodiment may contain a crosslinking agent. The crosslinking agent is not particularly limited as long as it is capable of crosslinking the polymer (which can be chemically bonded to the polymer) by the action of the active chemical species generated by the photopolymerization initiator. The cross-linking agent can form a bond by reacting the cross-linking agent with each other instead of chemically bonding with the polymer.

The crosslinking agent is preferably a multifunctional compound having two or more polymerizable double bonds in one molecule, and a multifunctional (meth)acrylic acid having two or more (meth)acryloyl groups in one molecule. The compound is more preferable (wherein, the crosslinking agent is not equivalent to the aforementioned polymer). From the viewpoints of uniform curability and further improvement of sensitivity, it is preferable to use a crosslinking agent having a crosslinkable group (polymerizable double bond) of the same kind as that of the polymer. The upper limit of the number of functions (number of polymerizable double bonds) per molecule of the crosslinking agent is not particularly limited, and is, for example, 8 or less, preferably 6 or less.

As a crosslinking agent, the following can be mentioned specifically,.

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 Base) acrylate, hexanediol di(meth)acrylate, cyclohexane dimethanol di(meth)acrylate, bisphenol A alkylene oxide two (meth)acrylate, bisphenol F alkylene oxide two (Meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerol tri(meth)acrylate, neopentaerythritol tetra(meth)acrylate Base) acrylate, dineopentyl erythritol penta(meth)acrylate, dineopentol hexa(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, Ethylene oxide addition ditrimethylolpropane tetra (meth) acrylate, ethylene oxide addition neopentyl erythritol tetra (meth) acrylate, ethylene oxide addition dineopentaerythritol hexa (Meth) acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, propylene oxide addition ditrimethylolpropane tetra(meth)acrylate, propylene oxide addition new Pentaerythritol tetra(meth)acrylate, propylene oxide addition, dineopentaerythritol hexa(meth)acrylate, ε-caprolactone addition, trimethylolpropane tri(meth)acrylate, ε -Caprolactone addition ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone addition neopentylerythritol tetra(meth)acrylate, ε-caprolactone addition Multifunctional (meth)acrylates such as alcohol hexa (meth)acrylate.

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, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerol trivinyl ether, neopentyl four Alcohol tetravinyl ether, dineopentaerythritol pentavinyl ether, dineopentaerythritol hexavinyl ether, ethylene oxide addition trimethylolpropane trivinyl ether, ethylene oxide addition two or three Multifunctional vinyl ethers such as methylol propane tetravinyl ether, ethylene oxide addition neopentyl erythritol tetravinyl ether, ethylene oxide addition dineopentaerythritol hexavinyl ether, etc.

2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, (meth)acrylic acid 2 -Vinyloxypropyl, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, (methyl) ) 6-vinyloxyhexyl acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(meth)acrylate Vinyl ether group-containing (meth)acrylates such as (vinyloxyethoxy)ethyl and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate.

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diene Propyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether , Glycerol triallyl ether, neopentyl erythritol tetraallyl ether, dineopentyl erythritol pentaallyl ether, dineopentaerythritol hexaallyl ether, ethylene oxide addition trimethylol Propane triallyl ether, ethylene oxide addition ditrimethylolpropane tetraallyl ether, ethylene oxide addition neopentyl erythritol tetraallyl ether, ethylene oxide addition dinepentyl ether Multifunctional allyl ethers such as tetraol hexaallyl ether.

(Meth)acrylates containing allyl groups, such as allyl (meth)acrylate. Tris (propylene oxyethyl) trimer isocyanate, tris (methacryloyloxy ethyl) trimer isocyanate, alkylene oxide addition Tris (propylene oxyethyl) trimer isocyanate, alkylene oxide addition Tris (methacryloxyethyl) trimer isocyanate and other trimeric isocyanates containing polyfunctional (meth)acrylic groups. Trimeric isocyanates having polyfunctional allyl groups such as triallyl isocyanate. Toluene diisocyanate, isophorone diisocyanate, dimethylene diisocyanate, etc. are combined with polyfunctional isocyanate and 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. ( Polyfunctional (meth)acrylate (urethane (meth)acrylate) obtained by the reaction of meth)acrylates. Multifunctional aromatic vinyls such as divinylbenzene.

Among them, trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, neopentaerythritol tetra(meth)acrylate, di-tris Tetrafunctional (meth)acrylates such as methylolpropane tetra(meth)acrylate and hexafunctional (meth)acrylates such as dineopentaerythritol hexa(meth)acrylate are preferred.

When the photosensitive resin composition contains a crosslinking agent, the photosensitive resin composition may contain only 1 type of crosslinking agent, and may contain 2 or more types of crosslinking agents. When the photosensitive resin composition contains a crosslinking agent, the amount may be appropriately set according to the purpose or application. As an example, the amount of the crosslinking agent can be generally 30 to 70 parts by mass, and preferably 40 to 60 parts by mass relative to 100 parts by mass of the polymer.

(Colorant) The photosensitive resin composition of this embodiment can contain a coloring agent. The composition contains a colorant, and thereby can be preferably used as a material for forming a color filter of a display device or an imaging element. As the coloring agent, various pigments or dyes can be used.

系顏料、吡咯亞甲基（pyrromethene）系顏料、染料色澱系顏料等。 作為無機顏料，能夠使用白色、體質顏料(氧化鈦、氧化鋅、硫化鋅、黏土、滑石、硫酸鋇、碳酸鈣等)、彩色顏料(鉻黃、鎘系、鉻朱紅(chrome vermilion)、鎳鈦、鉻鈦、黃色氧化鐵、紅丹、鉻酸鋅、鉛丹、群青、鐵藍、鈷藍、鉻綠、氧化鉻、釩酸鉍等)、發亮材料顏料(珍珠顏料、鋁顏料、青銅顏料等)、螢光顏料(硫化鋅、硫化鍶、鋁酸鍶等)等。As the pigment, organic pigments or inorganic pigments can be used. As organic pigments, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, Diketopyrrolopyrrole pigments, thioindigo pigments, anthraquinone pigments, quinoline yellow pigments, metal complex pigments, diketopyrrolopyrrole pigments,

Pigments, pyrromethene pigments, dye lake pigments, etc. As inorganic pigments, white, extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), color pigments (chrome yellow, cadmium series, chrome vermilion), nickel titanium can be used , Chrome titanium, yellow iron oxide, red lead, zinc chromate, lead lead, ultramarine blue, iron blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), brightening material pigments (pearl pigments, aluminum pigments, bronze Pigments, etc.), fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.), etc.

As the dye, for example, known dyes described in JP 2003-270428 A, JP 9-171108 A, and JP 2008-50599 A can be used.

Colorants (especially pigments) can be used with appropriate average particle diameters according to the purpose or use. Particularly when transparency as a color filter is required, a smaller average particle size of 0.1 μm or less is preferable. On the other hand, when concealment properties of paint or the like are required, a larger average particle size of 0.5 μm or more is preferable. The colorant can also be subjected to surface treatments such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc., depending on the purpose and application.

When the photosensitive resin composition contains a coloring agent, the photosensitive resin composition may contain only 1 type of coloring agent, and may contain 2 or more types of coloring agents. When the photosensitive resin composition contains a coloring agent, the amount may be appropriately set according to the purpose or use. However, considering the balance of the coloring concentration and the dispersion stability of the coloring agent, it is non-volatile with respect to all photosensitive resin compositions The components (components other than the solvent) are preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 50% by mass.

(Sunscreen) The photosensitive resin composition of this embodiment can contain a light-shielding agent. The composition contains a light-shielding agent, whereby it can be preferably used as a black matrix forming material of a display device or an imaging element. As the light-shielding agent, a well-known light-shielding agent can be used without particular limitation. For example, black pigments such as carbon black, bone black, graphite, iron black, and titanium black can be used as the sunscreen.

When the photosensitive resin composition contains a light-shielding agent, the amount may be appropriately set according to the purpose or application. However, considering the compatibility of light-shielding performance and the dispersion stability of the light-shielding agent, it is non-volatile with respect to all photosensitive resin compositions The components (components other than the solvent) are preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 50% by mass.

(Other ingredients) The photosensitive resin composition of this embodiment may contain components other than the above according to various purposes or required characteristics. Examples of components that may be contained include fillers, binder resins other than the above-mentioned polymers, polyfunctional (meth)acrylate compounds, acid generators, heat resistance improvers, development aids, plasticizers, and polymerizers. Inhibitors, UV absorbers, antioxidants, matting agents, defoamers, leveling agents, surfactants, antistatic agents, dispersants, slipping agents, surface modifiers, thixotropic agents, silanes Coupling agents, polyphenol compounds, etc.

<Pattern, color filter, black matrix, display device, imaging device, and display device or imaging device manufacturing method> The photosensitive resin composition is used to form a film, and the film can be exposed and developed to form a pattern. This pattern is suitable for, for example, color filters or black matrices. Specifically, a color filter can be obtained by forming a pattern using a photosensitive resin composition containing a colorant. In addition, by forming a pattern using a photosensitive resin composition containing a light-shielding agent, a black matrix can be obtained. Furthermore, it is possible to manufacture a display device (typically a liquid crystal display device) or an imaging element (typically a solid-state imaging device) equipped with a color filter and/or a black matrix

The typical steps of pattern formation are described below.

• Formation of photosensitive resin film For example, the photosensitive resin composition of this embodiment is coated on an arbitrary substrate, and it is dried as needed. By this, first, a photosensitive resin film is obtained.

The substrate is not particularly limited. For example, glass substrates, silicon wafers, ceramic substrates, aluminum substrates, SiC wafers, GaN wafers, copper clad laminates, etc. can be cited. The substrate may be an unprocessed substrate or a substrate with electrodes or elements formed on the surface. In order to improve adhesion, the substrate may be surface-treated. The coating method of the photosensitive resin composition is not specifically limited. Coating can be performed by spin coating using a spinner, spray coating using a sprayer, dipping, printing, roll coating, inkjet method, etc.

The drying of the photosensitive resin composition applied on the substrate is typically heated by a hot plate, hot air, oven, or the like. The heating temperature is usually 80 to 140°C, preferably 90 to 120°C. The heating time is usually 30 to 600 seconds, preferably about 30 to 300 seconds.

The thickness of the photosensitive resin film is not particularly limited, and may be appropriately adjusted according to the pattern finally obtained. The film thickness is usually 0.5 to 10 μm, preferably 1 to 5 μm. In addition, the film thickness can be adjusted depending on the content of the solvent in the photosensitive resin composition or the coating method.

• Exposure Exposure is typically performed by irradiating active light to the photosensitive resin film through an appropriate photomask. Examples of active rays include X-rays, electron beams, ultraviolet rays, and visible rays. From the viewpoint of wavelength, light of 200 to 500 nm is preferable. From the viewpoint of pattern resolution and operability, the g-ray, h-ray, or i-ray of a mercury lamp as the light source is preferred, and the i-ray is particularly preferred. In addition, two or more lights may be mixed and used. As the exposure device, a contact aligner, a mirror projecter, or a stepper is preferable. The amount of light for exposure may be appropriately adjusted depending on the amount of the photopolymerization initiator in the photosensitive resin film, the film thickness of the photosensitive resin film, or the like. The amount of exposure light is about 100 to 500 mJ/cm ^2, for example.

After exposure, the photosensitive resin film can be heated again as needed (post exposure heating: Post Exposure Bake). The heating temperature 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 of the active species generated by the photopolymerization initiator is promoted, and the hardening reaction is further promoted. That is, from the viewpoint of manufacturing process, higher sensitivity can be achieved.

•development The exposed photosensitive resin film is developed by an appropriate developer, whereby a pattern can be obtained, and a pattern-equipped substrate can be manufactured. In the development step, an appropriate developer can be used, and development can be performed using methods such as a dipping method, a paddle method, and a spin spray method. The pattern is obtained by removing the exposed portion (when it is a positive type) or the unexposed portion (when it is a negative type) of the photosensitive resin film by development and elution. When the photosensitive resin composition of this embodiment is used, a negative pattern is usually 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) aqueous inorganic alkali solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, and (ii) aqueous organic amine solutions such as ethylamine, diethylamine, triethylamine, and triethanolamine. , (Iii) Aqueous solutions of quaternary ammonium hydroxide such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Specific examples of the organic solvent include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) or butyl acetate, and ether solvents such as propylene glycol monomethyl ether. The developer may contain, for example, water-soluble organic solvents such as methanol and ethanol, or additives such as surfactants.

In this embodiment, it is preferable to use an aqueous alkali solution as the developer, and it is more preferable to use an aqueous solution of tetramethylammonium hydroxide or sodium carbonate. The concentration of the aqueous alkali solution is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

After development, various treatments can be performed. For example, after development, the pattern and/or the substrate can be cleaned by a rinse liquid. Examples of the rinse liquid include distilled water, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether. These can be used alone or in combination of two or more

In addition, the obtained pattern can be heated to fully harden it. The heating temperature is typically 150 to 400°C, preferably 160 to 300°C, more preferably 200 to 250°C. The heating time is not particularly limited, and is, for example, in the range of 15 to 300 minutes. The heating treatment can be performed by a heating plate, an oven, a temperature-rising oven capable of setting a temperature program, and the like. As the ambient gas when the heat treatment is performed, air or inert gas such as nitrogen or argon may be used. In addition, heating may be performed under reduced pressure.

Through the above steps, a pattern can be obtained and a patterned substrate can be manufactured. More specifically, a color filter can be obtained using a photosensitive resin composition containing a colorant. In addition, a black matrix can be obtained using a photosensitive resin composition containing a light-shielding agent. Furthermore, it is possible to manufacture a display device (typically a liquid crystal display device) or an imaging element (typically a solid-state imaging device) provided with a color filter and/or a black matrix.

FIG. 1 schematically shows an example of the structure of a display device and/or an imaging element provided with a color filter and/or a black matrix. A black matrix 11 and color filters 12 are formed on the substrate 10. In addition, a protective film 13 and a transparent electrode layer 14 are provided on the upper part of the black matrix 11 and the color filter 12. The substrate 10 is usually made of a material that transmits light. For example, it is composed of any one of glass, polyester, polycarbonate, polyolefin, polysulfide, and cyclic olefin polymer. The substrate 10 may be subjected to corona discharge treatment, ozone treatment, chemical treatment, or the like. The substrate 10 is made of glass, for example.

The black matrix 11 is usually a cured product of a photosensitive resin composition containing a light-shielding agent. As the color filter 12, there are usually three colors of red, green, and blue. The color filter 12 is usually a cured product of a photosensitive resin composition containing a coloring agent corresponding to each color.

The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above can be adopted. In addition, the present invention is not limited to the above-mentioned embodiment, and modifications, improvements, etc., within the range that can achieve the object of the present invention are also included in the present invention. [Example]

The embodiments of the present invention will be described based on examples and comparative examples. In addition, this invention is not limited to an Example.

The compounds used in the examples are sometimes represented by the following abbreviations or trade names. •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 left compound in the mixture measured by gas chromatograph is about 55% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

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

•A-9550: A mixture of the following two compounds. The amount of the right compound in the mixture estimated from the hydroxyl value is about 50% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

＜Synthesis of raw polymer＞ Firstly, a raw polymer containing maleic anhydride structural unit and 2-norbornene structural unit was synthesized. The details are shown below.

(Raw polymer 1) Weigh 353.02g of maleic anhydride (3.6mol), 338.94g of 2-norbornene (3.6mol) and 33.16g of dimethyl-2,2'-azobis(2-methylpropionic acid) Ester) (0.144mol) and put it into a reaction vessel of appropriate size equipped with a stirrer and a cooling tube. These were dissolved in a mixed solvent composed of 1030.1 g of methyl ethyl ketone and 113.0 g of toluene to prepare a solution. Nitrogen was passed through the solution for 30 minutes to remove oxygen, followed by heating at 65°C for 1.5 hours while stirring, and then heating at 80°C for 6 hours to polymerize maleic anhydride and 2-norbornene. Polymerization solution. The polymerization solution obtained above was dropped into 8519.9 g of methanol to precipitate a white solid. The obtained white solid was vacuum-dried at a temperature of 120° C. to obtain 607.5 g of a polymer (base polymer 1) having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. The polymer was measured by gel permeation chromatography (GPC), and 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) Weigh 353.02g of maleic anhydride (3.6mol), 338.94g of 2-norbornene (3.6mol) and 33.16g of dimethyl-2,2'-azobis(2-methylpropionic acid) Ester) (0.144mol) and put it into a reaction vessel of appropriate size equipped with a stirrer and a cooling tube. These were dissolved in a mixed solvent composed of 2654.9 g of MEK and 113.0 g of toluene to prepare a solution. This solution was dissolved in nitrogen for 30 minutes to remove oxygen, and then heated at 65°C for 1.5 hours while stirring, and then heated at 80°C for 6 hours to polymerize maleic anhydride and 2-norbornene. Polymerization solution. The polymerization solution obtained above was dropped into 1,3972.1 g of methanol to precipitate a white solid again. The obtained white solid was vacuum-dried at a temperature of 120°C to obtain 569.1 g of a polymer (base polymer 2) having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. As a result of GPC measurement of the obtained polymer, the weight average molecular weight Mw was 4300, and the polydispersity (weight average molecular weight Mw)/(number average molecular weight Mn) was 1.59.

<Synthesis of polymer (ring-opening of MA-derived structural unit of raw polymer)> (Comparative Synthesis Example 1) A polymer in which the MA-derived structural unit (hereinafter, also simply referred to as "MA unit") of the base polymer 1 was ring-opened using a hydroxyl-containing trifunctional acrylate was produced. The details will be described below. First, 64.15 g of MEK was added to 30 g of base polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, add 96.85g of A-TMM-3L (the amount of the above two mixtures, the same below) to this solution, then add 9.00g of triethylamine (0.089mol) and react at 70°C for 6 hours. The reaction solution.

The prepared reaction solution was treated with an aqueous formic acid solution to remove the water phase from the reaction solution. Then, the polymer was purified by the following steps. • Use excess toluene to precipitate the polymer again. • The polymer powder obtained by reprecipitation was repeatedly washed with excess toluene twice. • The polymer powder after the above 2 washings was washed with excess water 3 times.

In the above, 23.39 g of a polymer in which the structural unit derived from maleic anhydride in the base polymer was ring-opened with A-TMM-3L was obtained.

(Comparative Synthesis Example 2) A polymer in which the MA unit of the base polymer 1 was ring-opened with only a hydroxyl-containing monofunctional acrylate was produced. The details will be described below. First, 55.50 g of MEK was added to 30 g of base polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, 22.65 g of BHEA (0.195 mol) was added to this solution, and then 9.00 g of triethylamine (0.089 mol) was added, and the reaction was further performed at a temperature of 70° C. for 6 hours to prepare a reaction solution. The resulting reaction solution was treated with an aqueous formic acid solution to remove the water phase from the reaction solution. Then, the solution was poured into a large amount of pure water to precipitate a polymer. The obtained polymer was filtered and washed with pure water. In the above, 27.21 g of a polymer in which the structural unit derived from maleic anhydride in the base polymer was ring-opened only with BHEA was obtained.

(Comparative Synthesis Example 3) A polymer in which the MA unit of the base polymer 1 was ring-opened with only a hydroxyl-containing monofunctional acrylate was produced. The details will be described below. First, 55.50 g of MEK was added to 30 g of base polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, 28.11 g of 4-HBA (0.195 mol) was added to this solution, and then 9.00 g of triethylamine (0.089 mol) was added, and the reaction was carried out at a temperature of 70° C. for 6 hours to prepare a reaction solution. The resulting reaction solution was treated with an aqueous formic acid solution to remove the water phase from the reaction solution. Then, the solution was poured into a large amount of pure water to precipitate a polymer. The obtained polymer was filtered and washed with pure water. The above obtained 26.54 g of a polymer in which the structural unit derived from maleic anhydride in the raw polymer was ring-opened with 4-HBA.

(Synthesis example 1) A polymer in which the MA unit of the base polymer 1 was ring-opened with a hydroxyl-containing trifunctional acrylate and a hydroxyl-containing monofunctional acrylate was produced. The details will be described below. First, 67.72 g of MEK was added to 30 g of base polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, 58.12 g of A-TMM-3L was added to this solution, and then 9.00 g of triethylamine (0.089 mol) was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Then, 22.65 g of BHEA (0.195 mol) was further added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution. In the same manner as in Comparative Synthesis Example 1, the resulting reaction solution was purified with formic acid aqueous solution, excess toluene, excess water, and the like. Above, 22.21 g of a polymer in which the structural unit derived from maleic anhydride in the base polymer was ring-opened with A-TMM-3L and BHEA was obtained.

(Synthesis example 2) A polymer in which the MA unit of the base polymer 1 was ring-opened with a hydroxyl-containing trifunctional acrylate and a hydroxyl-containing monofunctional acrylate was produced. The details will be described below. First, 49.41 g of MEK was added to 30 g of base 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 of triethylamine (0.089 mol) was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Then, 22.65 g of BHEA (0.195 mol) was further added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution. In the same manner as in Comparative Synthesis Example 1, the resulting reaction solution was purified with formic acid aqueous solution, excess toluene, excess water, and the like. In the above, 22.53 g of a polymer in which the structural unit derived from maleic anhydride in the base polymer was ring-opened with A-TMM-3L and BHEA was obtained.

(Synthesis example 3) A polymer in which the MA unit of the base polymer 1 was ring-opened with a hydroxyl-containing trifunctional acrylate and a hydroxyl-containing monofunctional acrylate was produced. The details will be described below. First, 49.51 g of MEK was added to 30 g of base polymer 1 (0.156 mol in terms of MA) to prepare a solution. Next, after adding 19.37 g of A-TMM-3L to this solution, 18.00 g of triethylamine (0.178 mol) was added and reacted at a temperature of 70° C. for 2 hours. Then, 22.65 g of BHEA (0.195 mol) was further added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution. In the same manner as in Comparative Synthesis Example 1, the resulting reaction solution was purified with formic acid aqueous solution, excess toluene, excess water, and the like. The above obtained 22.10 g of a polymer in which the structural unit derived from maleic anhydride in the base polymer was ring-opened with A-TMM-3L and BHEA.

(Synthesis example 4) A polymer in which the MA unit of the base polymer 1 was ring-opened with a hydroxyl-containing trifunctional acrylate and a hydroxyl-containing monofunctional acrylate was produced. The details will be described below. First, 49.86 g of MEK was added to 30 g of base 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 of triethylamine (0.089 mol) was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Then, 28.13 g of 4-HBA (0.195 mol) was further added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution. In the same manner as in Comparative Synthesis Example 1, the resulting reaction solution was purified with formic acid aqueous solution, excess toluene, excess water, and the like. The above obtained 24.64g of a polymer in which the structural unit derived from maleic anhydride in the raw polymer was ring-opened with A-TMM-3L and 4-HBA

(Synthesis example 5) A polymer in which the MA unit of the base polymer 1 was ring-opened with a hydroxyl-containing trifunctional acrylate and a hydroxyl-containing monofunctional acrylate was produced. The details will be described below. First, 47.35 g of MEK was added to 30 g of base 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 of triethylamine (0.178 mol) was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Then, 28.13 g of 4-HBA (0.195 mol) was further added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution. In the same manner as in Comparative Synthesis Example 1, the resulting reaction solution was purified with formic acid aqueous solution, excess toluene, excess water, and the like. The above obtained 25.77 g of a polymer in which the structural unit derived from maleic anhydride in the base polymer was ring-opened with A-TMM-3L and 4-HBA.

(Synthesis example 6) A polymer in which the MA unit of the base polymer 1 was ring-opened with a hydroxyl group-containing 5-functional acrylate and a hydroxyl group-containing monofunctional acrylate was produced. The details will be described below. First, 71.03 g of MEK was added to 30 g of base 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 of triethylamine (0.089 mol) was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Then, 22.65 g of BHEA (0.195 mol) was further added to the reaction solution and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution. In the same manner as in Comparative Synthesis Example 1, the resulting reaction solution was purified with formic acid aqueous solution, excess toluene, excess water, and the like. The above obtained 25.51g of a polymer in which the structural unit derived from maleic anhydride in the base polymer was ring-opened with A-9550 and BHEA.

(Synthesis example 7) A polymer in which the MA unit of the base polymer 2 was ring-opened with a hydroxyl-containing trifunctional acrylate and a hydroxyl-containing monofunctional acrylate was produced. The details will be described below. First, 49.41 g of MEK was added to 30 g of base 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 of triethylamine (0.089 mol) was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Then, 22.65 g of BHEA (0.195 mol) was further added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution. In the same manner as in Comparative Synthesis Example 1, the resulting reaction solution was purified with formic acid aqueous solution, excess toluene, excess water, and the like. In the above, 21.11 g of a polymer in which the structural unit derived from maleic anhydride in the base polymer was ring-opened with A-TMM-3L and BHEA was obtained.

(Synthesis example 8) A polymer in which the MA unit of the base polymer 1 was ring-opened with a hydroxyl-containing trifunctional acrylate and a hydroxyl-containing monofunctional acrylate was produced. The details will be described below. First, 50.60 g of MEK was added to 30 g of base 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 of triethylamine (0.089 mol) was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Then, 22.65 g of BHEA (0.195 mol) was further added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution. In the same manner as in Comparative Synthesis Example 1, the resulting reaction solution was purified with formic acid aqueous solution, excess toluene, excess water, and the like. The above obtained 20.66 g of a polymer in which the structural unit derived from maleic anhydride in the base polymer was ring-opened with A-TMM-3LM-N and BHEA.

(Synthesis Example 9) A polymer in which the MA unit of the base polymer 1 was ring-opened with a hydroxyl-containing trifunctional acrylate and a hydroxyl-containing monofunctional acrylate was produced. The details will be described below. First, 46.60 g of MEK was added to 30 g of base 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 then 18.00 g of triethylamine (0.178 mol) was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Then, 22.65 g of BHEA (0.195 mol) was further added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution. In the same manner as in Comparative Synthesis Example 1, the resulting reaction solution was purified with formic acid aqueous solution, excess toluene, excess water, and the like. The above obtained 21.22 g of a polymer in which the structural unit derived from maleic anhydride in the base polymer was ring-opened with A-TMM-3L and BHEA.

(Synthesis example 10) A polymer in which the MA unit of the base polymer 1 was ring-opened with a hydroxyl-containing trifunctional acrylate and a hydroxyl-containing monofunctional acrylate was produced. The details will be described below. First, 54.13 g of MEK was added to 30 g of base 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 then 18.00 g of triethylamine (0.178 mol) was added, and the reaction was carried out at a temperature of 70°C for 2 hours. Then, 22.65 g of BHEA (0.195 mol) was further added and reacted at a temperature of 70° C. for 4 hours to prepare a reaction solution. In the same manner as in Comparative Synthesis Example 1, the resulting reaction solution was purified with formic acid aqueous solution, excess toluene, excess water, and the like. In the above, 24.54 g of a polymer in which the structural unit derived from maleic anhydride in the base polymer was ring-opened 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 as a polystyrene standard material. In addition, the disappearance of the peaks of acrylate compounds (BHEA, 4-HBA, A-TMM-3L, A-TMM-3LM-N, A-9550) was confirmed by GPC measurement. That is, it was confirmed that in the polymers of the respective synthesis examples and comparative synthesis examples, acrylates that did not react with the MA units of the base polymer or acrylate compounds that did not react with the MA units at the beginning (hydroxyl-free acrylates) Is fully removed.

<NMR measurement of polymer> ¹ H-NMR measurement was performed on the polymers of each synthesis example and comparative synthesis example. Based on the integrated value of the 4H peak (near 8.1 ppm) of the phenyl group of the internal standard dimethyl terephthalate measured by ¹ H-NMR, and based on the H peak (12.4 ppm) of the carboxyl group (-COOH) of the polymer Near the integral value of) the amount of carboxyl groups is calculated. Furthermore, the acid value (mgKOH/g) was calculated from this amount. The larger the acid value, the larger the amount of carboxyl groups per unit mass of the polymer.

Also, similarly, based on the integrated value of the 4H peak (near 8.1 ppm) of the phenyl group of dimethyl terephthalate, based on the propylene moiety (CH ₂ =CH-COO-) in the polymer The integrated value of the 3H peak (near 6.2ppm) is the amount of C=C double bond, and the double bond equivalent is calculated based on this amount (C=C double bond per mole of polymer mass, g/mol) . The smaller the value of the double bond equivalent, the greater the amount of C=C double bonds per unit mass of the polymer.

Table 1 collectively shows the acrylate compound used in the synthesis of the polymers of the respective synthesis examples and comparative synthesis examples, and the weight average molecular weight, degree of dispersion, acid value, and double bond equivalent of the polymer.

In addition, R ^{D in the} first structural unit is the ratio of the structural unit of a group containing two or more polymerizable carbon-carbon double bonds, and R ^{D in the} first structural unit contains only one polymerizable carbon-carbon double bond The ratio of the structural unit of the group (the ratio of the total structural unit of the polymer) is also shown in Table 1. These ratios are based on the premise that the ratio of the norbornene structural unit: the maleic anhydride structural unit in the raw polymer 1 or 2 is 50:50 (molar ratio), as described above by solving the "simultaneous equation", etc. And find out. Wherein, the sum of these two ratios in each polymer is less than 50 mol%. Therefore, it can be said that not all of the maleic anhydride structural units in the polymer are ring-opened but a part of them still has a structure represented by the formula (MA).

[Table 1] polymer Comparative Synthesis Example 1 Comparative Synthesis Example 2 Comparative Synthesis Example 3 Synthesis example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Use acrylic A-TMM-3L (3 functions) BHEA (monofunctional) 4-HBA (monofunctional) A-TMM-3L (3-functional) BHEA (monofunctional) A-TMM-3L (3-functional) BHEA (monofunctional) A-TMM-3L (3-functional) BHEA (monofunctional) A-TMM-3L (3-functional) 4-HBA (monofunctional) Weight average molecular weight Mw 15100 7000 9800 11700 11700 14100 16,300 Dispersion 1.87 1.76 2.05 1.80 1.88 2.08 1.98 Acid value (mgKOH/g) 68 103 113 86 95 100 98 Double bond equivalent (g/mol) 286 537 530 348 378 323 367 R ^D contains more than 2 C=C structural units (mol% in all polymers) 18 0 0 9 6 9 7 R ^D contains only 1 C=C structural unit (mol% in all polymers) 0 twenty three 27 12 16 16 18 polymer Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 Synthesis Example 10 Use acrylic A-TMM-3L (3-functional) 4-HBA (monofunctional) A-9550 (5-functional) BHEA (monofunctional) A-TMM-3LM-N (3-functional) BHEA (monofunctional) A-TMM-3LM-N (3-functional) BHEA (monofunctional) A-TMM-3L (3-functional) BHEA (monofunctional) A-TMM-3LM-N (3-functional) BHEA (monofunctional) Weight average molecular weight Mw 17,300 12600 8200 11400 11000 17,600 Dispersion 2.10 3.45 1.74 1.78 1.72 2.33 Acid value (mgKOH/g) 101 72 110 104 126 72 Double bond equivalent (g/mol) 323 348 325 459 358 311 R ^D contains more than 2 C=C structural units (mol% in all polymers) 10 6 8 2 4 11 R ^D contains only 1 C=C structural unit (mol% in all polymers) 18 12 20 twenty two 28 15

Here, the acid value and double bond equivalent values of the polymers of Synthesis Examples confirm that the polymers of Synthesis Examples 1 to 10 contain the structural unit represented by the general formula (1), that is, R ^D contains two or more The structural unit of the group of polymerizable carbon-carbon double bond. This situation will be described below.

Consider using a compound having a hydroxyl group and a polymerizable carbon-carbon double bond to open the ring of the MA unit in the base polymer. A compound with one molecule of hydroxyl group and polymerizable carbon-carbon double bond opens one MA unit to generate one carboxyl group as shown in the general formula (1). Among them, when a compound having a hydroxyl group and a polymerizable carbon-carbon double bond such as BHEA or 4-HBA is a monofunctional compound, the number of C=C double bonds introduced is one. That is, by ring opening of one MA unit, one carboxyl group increases, and one C=C double bond increases.

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

In this way, among two or more polymers with the same acid value (that is, the ring-opening amount of the MA unit is the same), the double bond equivalent of the polymer in which the MA unit is ring-opened with a polyfunctional compound is higher than that of the monofunctional polymer The compound has a small double bond equivalent to open the MA unit of the polymer.

Based on this situation, confirm the above table. The acid value of the polymers of Synthesis Examples 1 to 10 (corresponding to the amount of carboxyl group generated based on ring opening) is equal to the acid value of the polymers of Comparative Synthesis Examples 2 and 3 (only monofunctional compounds are used to open the MA unit) Or smaller. Nevertheless, the double bond equivalents of the polymers of Synthesis Examples 1 to 10 tended to be smaller than those of the polymers of Comparative Synthesis Examples 2 and 3 (that is, the C=C double bond equivalent per unit mass of the polymer Large amount). This means that the polymers of Synthesis Examples 1 to 10 have introduced structures derived from polyfunctional compounds such as A-TMM-3L or A-9550.

It is clear from the synthesis steps that the structure derived from a polyfunctional compound such as A-TMM-3L or A-9550 is introduced into the base polymer. However, as mentioned above, the relationship between the acid value and the double bond equivalent also proves that it is derived from polyfunctional Introduction of the structure of the compound.

＜Evaluation＞ [Developability evaluation] (Dissolution rate of polymer in TMAH aqueous solution) The polymers of each synthesis example and comparative synthesis example were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution with a solid content concentration of 30% by mass. Next, the above solution was spin-coated on the wafer, the PGMEA was dried, and then pre-baked at a temperature of 100° C. for 2 minutes to produce a resin film with a film thickness of about 2 μm. The resin film and the wafer were immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution at a temperature of 23° C., and the dissolution rate of the resin film was measured. The dissolution rate was calculated by visually observing the immersed wafer and measuring the time until the resin film was dissolved and the interference pattern was not seen, and the film thickness was divided by the time.

The developability was judged based on the following criteria. ○(Good): The dissolution rate is 500nm/s or more × (poor): the dissolution rate is less than 500nm/s

[Sensitivity evaluation] (2.0% by mass sodium carbonate aqueous solution) First, a photosensitive resin composition in which the following components were dissolved in propylene glycol monomethyl ether acetate (PGMEA) so that the total solid content concentration became 30% by mass was obtained. •Polymer (polymers of Synthesis Examples 1 to 10 or Comparative Synthesis Examples 1 to 3): 100 parts by mass • Multifunctional acrylate (dineopentaerythritol hexaacrylate): 50 parts by mass • Photopolymerization initiator (made 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 (Hexamethy Idisilazane: hexamethyldisilazane), and baked on a hot plate at 100°C for 120 seconds. Film A about 3.0μm thick (±0.3μm). The film A was exposed to 100mJ/cm ² by using a g+h+i-ray mask alignment exposure machine (PLA-501F) made by Canon Inc. through a mask with a gray scale of 1-100%. The amount of exposure is g+h+i rays. After exposure, the film was developed with a 2.0% by mass sodium carbonate aqueous solution at 23° C. for 60 seconds (including wafer immersion) to obtain film B exposed and developed at each exposure amount of 1-100 mJ/cm ² .

Based on the film thicknesses of film A and film B obtained by the above method, the residual film rate was calculated by the following formula. Residual film rate (%) = (film thickness of film B under each exposure amount/film thickness of film A)×100 Furthermore, the exposure amount at which the residual film rate becomes 95% or more is used as the sensitivity of each photosensitive resin composition The evaluation was performed based on the following criteria. ◎(Very good sensitivity): 20mJ/cm ² or less ○(Good sensitivity): 21～50mJ/cm ² × (Poor sensitivity): 51mJ/cm ² or more

[Developability evaluation] (addition: the dissolution rate of polymer in Na ₂ CO ₃ aqueous solution) In order to explore the adaptability to various development processes, the developability when sodium carbonate aqueous solution is used as the developer Evaluation. Specifically, for the photosensitive resin composition prepared in the above-mentioned [Sensitivity Evaluation], any polymer in Synthesis Examples 1 to 10 was used as the polymer, and 2.0% by mass sodium carbonate was used as the developer. The aqueous solution was used as a procedure, and the production of the resin film and the measurement of the dissolution rate were performed in the same manner as in the above-mentioned [Developability Evaluation]. Furthermore, it evaluated based on the following criteria. ○ (good): dissolution rate of 50nm/s or more × (poor): dissolution rate of less than 50nm/s

The evaluation results are summarized below.

[Table 2] Example/Comparative Example No. Comparative example 1 Comparative example 2 Comparative example 3 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Use polymer Comparative Synthesis Example 1 Comparative Synthesis Example 2 Comparative Synthesis Example 3 Synthesis example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 Synthesis Example 10 Evaluation Development (TMAH developer) X ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Sensitivity ◎ X X ◎ ○ ◎ ◎ ◎ ◎ ○ ○ ○ ○ Developability (Na ₂ CO ₃ developer) X ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

As shown in Table 2, in the evaluation using the polymers of Synthesis Examples 1 to 10, both the developability and the sensitivity were good. That is, it is possible to have both sensitivity and developability. In particular, the developability was good not only when TMAH developer was used, but also when sodium carbonate developer was used. It can be seen that the photosensitive resin composition or polymer of this embodiment has good solubility in various developing solutions.

On the other hand, in the evaluation using the polymer of Comparative Synthesis Example 1, the developability was poor. It is considered that although the polymer contains relatively many polymerizable carbon-carbon double bonds (double bond equivalent: 286 g/mol), the acid value is less than 70 mgKOH/g, and sufficient developability is not obtained. In addition, in the evaluation using the polymers of Comparative Synthesis Examples 2 and 3, the sensitivity was poor. It is considered that the reason for this is that there are no double bonds of the density required for high sensitivity in the polymer.

＜Production of color filter＞ The photosensitive resin composition prepared in [Sensitivity Evaluation] contains the polymer of Synthesis Example 1 and further added an appropriate amount of pigment dispersion NX-061 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., Green) colored photosensitive resin composition. A film was formed on the substrate, and exposure, alkali development, etc. were performed to form a green color filter. In addition, as a pigment dispersion, instead of NX-061, NX-053 (blue), NX-032 (red) manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., etc. were used to form a blue or red color filter. . Incidentally, these color filters are sufficiently resistant to high temperatures that may be exposed during the equipment manufacturing process. It is believed that this is related to the fact that the polymer contains a structural unit having a cyclic hydrocarbon skeleton.

＜Creation of black matrix＞ For the photosensitive resin composition prepared in [Sensitivity Evaluation] that contains the polymer of Synthesis Example 1, an appropriate amount of carbon black dispersion NX-595 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. was added ) Black photosensitive resin composition. This was formed into a film on a substrate, and exposure, alkali development treatment, etc. were performed to form a black matrix. Incidentally, the black matrix is sufficiently resistant to high temperatures that may be exposed during the equipment manufacturing process. It is believed that this is related to the fact that the polymer contains a structural unit having a cyclic hydrocarbon skeleton.

This application is based on the priority of Japanese Patent Application No. 2019-015715 filed in Japan on January 31, 2019, and uses all the disclosures here.

10: substrate 11: black matrix 12: Color filter 13: Protective film 14: Transparent electrode layer

The above objectives and other objectives, features and advantages are further clarified by the preferred embodiments described below and the accompanying drawings.

Fig. 1 is a diagram (cross-sectional view) schematically showing an example of the structure of a liquid crystal display device and/or a solid-state imaging element.

10: substrate

11: black matrix

12: Color filter

13: Protective film

14: Transparent electrode layer

Claims (23)

A photosensitive resin composition comprising 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 the general formula (1), R ^D is a group containing a polymerizable carbon-carbon double bond. The photosensitive resin composition of claim 1, wherein the first structural unit includes a structural unit in which the R ^D is a group containing two or more polymerizable carbon-carbon double bonds. The photosensitive resin composition of claim 1 or 2, wherein the first structural unit includes: R ^D is a structural unit containing two or more polymerizable carbon-carbon double bonds, and R ^D contains only A structural unit of a polymerizable carbon-carbon double bond group. The photosensitive resin composition of claim 1, wherein the aforementioned polymer further includes a second structural unit represented by the following formula (MA),

. Such as the photosensitive resin composition of claim 1, wherein The aforementioned polymer also contains a structural unit having a cyclic hydrocarbon skeleton. Such as the photosensitive resin composition of claim 1, wherein The ratio of the first structural unit in the total structural unit of the polymer is 10 to 40 mol%. Such as the photosensitive resin composition of claim 1, wherein The weight average molecular weight of the aforementioned polymer is 6,000-25,000. The photosensitive resin composition of claim 1, which further contains a colorant. The photosensitive resin composition of claim 1, which further contains a sunscreen agent. A polymer having a first structural unit represented by the following general formula (1), an acid value of 70-300 mgKOH/g, and a double bond equivalent of 100-500 g/mol,

In the general formula (1), R ^D is a group containing a polymerizable carbon-carbon double bond. Structural units to carbon double bond group - such as a polymer of 10, wherein the first structural unit R ^D comprises a system containing two or more polymerizable carbon request entry. The polymer of claim 10 or 11, wherein the first structural unit includes: R ^D is a structural unit of a group containing two or more polymerizable carbon-carbon double bonds, and R ^D contains only one polymer The structural unit of the radical carbon-carbon double bond. Such as the polymer of claim 10, which further comprises a second structural unit represented by the following formula (MA),

. Such as the polymer of claim 10, which further comprises a structural unit having a cyclic hydrocarbon skeleton. Such as the polymer of claim 10, in which, The ratio of the aforementioned first structural unit in the total structural unit is 10-40 mol%. For example, the polymer of claim 10 has a weight average molecular weight of 6,000-25,000. A pattern obtained using the photosensitive resin composition of claim 1. A color filter obtained by using the photosensitive resin composition of claim 8. A display device is provided with the color filter of claim 18. An imaging element provided with the color filter of claim 18. A black matrix obtained using the photosensitive resin composition of claim 9. A display device is provided with the black matrix of claim 21. An imaging element having the black matrix of claim 21.

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