JP5115002B2 - Polymerizable compound, polymer compound using the same, and resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable compound resistant to decomposition during heating, having excellent solubility and soluble in an alkali. <P>SOLUTION: The polymerizable compound comprises a compound having one or more polymerizable unsaturated bonds in one molecule and expressed by formula (1). In the formula (1), at least one of R<SP>1</SP>to R<SP>4</SP>is a substituent containing a polymerizable unsaturated bond; the other groups of R<SP>1</SP>to R<SP>4</SP>are each independently a hydrogen atom, a halogen atom, a hydroxy group, an amino group or a univalent organic group; and R<SP>5</SP>to R<SP>10</SP>are each independently a hydrogen atom, a halogen atom or a univalent organic group. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a polymerizable compound, a polymer compound using the same, a resin composition containing the polymerizable compound, and an article using the same. More specifically, the present invention is a polymerizable compound that exhibits high solubility, is not easily decomposed by heating, and particularly has a carboxyl group-containing structure, and is excellent in solubility in an aqueous alkali solution. High heat resistance and high stability at least partly formed by a resin composition with less generation of decomposition products by heating, a photosensitive resin composition containing the polymerizable compound, and a cured product of the resin composition Related to the article.

Photosensitive resins that cure or change solubility upon irradiation with radiation such as ultraviolet rays are generally those having good solubility in the exposed area (positive type) and those having good solubility in the unexposed area (negative). Type). In the case of the negative type, since the photosensitive resin itself is cured and becomes insoluble by exposure, the photosensitive resin often remains on the substrate and becomes a part of the product as a functional film.
Negative-type photosensitive resins have been used initially in, for example, paints, printing inks, overcoat layers, adhesives, printing masters, etc., but in recent years, solder resists for wiring protection of printed wiring boards, interlayer insulating films, Applications have expanded to resists for forming color filter pixels, antireflection films, holograms, and the like.

  One of the commonly used negative photosensitive resins is a compound having one or more ethylenically unsaturated bonds, a photoradical initiator that generates radicals by light irradiation, and developability and coating as required. There is a resin composition in which a polymer compound that imparts film flexibility, an inorganic filler, a pigment, and the like are blended. When this composition is irradiated with radiation, a compound having an ethylenically unsaturated bond is bonded by a radical reaction, and is cured with a large molecular weight.

  In addition, after changing the solubility by exposing these photosensitive resin compositions, treatment with an organic solvent, water, an alkaline or acidic aqueous solution, etc. results in an exposed area (positive type) or unexposed. Only the exposed portion (negative type) can be removed to obtain a desired pattern image. As the treatment liquid, an aqueous solution, particularly an alkaline aqueous solution is often selected from the viewpoint of environmental burden, cost, and working environment.

Resist of the type that develops with an alkaline aqueous solution contains a component having a carboxyl group or a phenolic hydroxyl group in order to impart developability or a latent substituent in the composition that gives a carboxyl group or a phenolic hydroxyl group after exposure. There are many things that come out.
For general resists, a polymer compound is used as a structure that imparts such developability, and other low molecular weight components constituting the resist have a site that gives solubility or affinity to an alkaline aqueous solution. It is rare to use something that includes it.

  In general, a compound containing at least one ethylenically unsaturated bond, which is a component constituting a negative photosensitive resin composition, is highly hydrophobic and difficult to dissolve in an alkaline aqueous solution as a developer. May remain and cause problems. In order to solve these problems, for example, a compound having an ethylenically unsaturated bond and a carboxyl group having the following structure has been proposed. However, since this compound is an aliphatic hydrocarbon skeleton, there is a problem that it is inferior in heat resistance.

  On the other hand, a hydrophilic and alkali-soluble carboxyl can be obtained by reacting an acid anhydride with a compound having an ethylenically unsaturated bond and a hydroxyl group to form a half ester, such as Patent Document 1 and Patent Document 2. Attempts have been made to introduce groups. Examples of acid anhydrides that form a half ester include, for example, Patent Document 2, saturated or unsaturated acid anhydrides, specifically maleic anhydride, phthalic anhydride, succinic anhydride, tetrahydrophthalic anhydride, and anhydrous. Illustrative examples include oxahydrophthalic acid, trimellitic anhydride, het acid anhydride, methyl nadic anhydride, itaconic anhydride, benzophenone tetracarboxylic anhydride, and the like.

Among these, the polymerizable compound having a half ester moiety obtained by using a saturated acid anhydride such as succinic anhydride or hexahydrophthalic anhydride is more heat resistant than the half ester compound obtained by an unsaturated acid anhydride. There was a problem of inferiority.
On the other hand, the half ester structure obtained from the unsaturated acid anhydride has higher heat resistance than the half ester structure obtained using the saturated acid anhydride, but the unsaturated acid anhydride is an acid anhydride having an intramolecular conjugated structure. Since it is stable when it has a group, a reaction for synthesizing a half ester from a compound having an unsaturated acid anhydride and a hydroxyl group is a reversible reaction. Therefore, the half ester compound obtained from the unsaturated acid anhydride having an acid anhydride group having an intramolecular conjugated structure is decomposed into a compound having an original acid anhydride and a hydroxyl group by heating (the following formula (3) ). Therefore, a compound having a half ester site obtained from a conventional unsaturated acid anhydride causes deterioration of the coating film containing it with heating, or the unsaturated acid anhydride volatilizes and pollutes the surrounding environment. There was a problem such as.

  Decomposition of the polymerizable compound causes deterioration of light resistance, coloring and fading, peeling of the coating film, generation of cracks, etc., and final products such as interlayer insulating films and solder resists for electronic parts, pixel forming resists for color filters. There is a problem that it causes a decrease in reliability.

In particular, display parts such as color filters for liquid crystal displays and electronic parts such as solder resists for printed wiring boards have a heating process of 150 ° C or higher during the manufacturing process, which requires a higher level of reliability. In addition, the heat resistance of the members constituting them, deterioration of the film after heating, the presence or absence of volatile components at the time of heating are severe, and improvement to reduce the residue at the time of development is necessary, as well as heat resistance and low outgas Such characteristics are required.
In addition, as an attempt to improve the heat resistance of the polymerizable compound, the use of an aromatic compound as a skeleton has been studied, but when an aromatic compound such as a benzene skeleton is used as the skeleton, the solubility in a solvent There was a tendency to be incompatible with other components.

Japanese Patent Publication No. 1-54390 JP-A-8-259663

The present invention has a high heat resistance, is particularly difficult to decompose during heating, hardly generates outgas, and has excellent solubility and compatibility, and a resin composition containing the same, and the same The primary purpose is to provide articles.
In addition, a second object of the present invention is to provide an alkali-soluble polymerizable compound, a resin composition containing the same, and an article using the same, which have an improved affinity for an alkaline aqueous solution.

  In order to solve the first object, the polymerizable compound provided by the present invention is a polymerization comprising a compound having one or more polymerizable unsaturated bonds in one molecule, represented by the following formula (1). It is a sex compound.

（式（１）において、Ｒ^１〜Ｒ^４のうち少なくとも１つは、下記式（２）で表される構造を有する重合性不飽和結合を含有する置換基である。一分子内に２つ以上の前記重合性不飽和結合を含有する置換基が存在する場合、それらは互いに同一であっても異なっていても良い。また、Ｒ^１〜Ｒ^４のうち前記重合性不飽和結合を含有する置換基でないものはそれぞれ独立に水素原子、ハロゲン原子、水酸基、アミノ基、置換基を有していても良いアルコキシ基、置換基を有していても良いアリールオキシ基、或いは、置換基を有していても良い直鎖、分岐又は環状のアルキル基であって、前記置換基は、ハロゲン原子、水酸基、メルカプト基、シアノ基、シリル基、シラノール基、ニトロ基、不飽和アルキルエーテル基、アリールエーテル基、不飽和アルキルチオエーテル基、及びアリールチオエーテル基よりなる群からされる１種以上である。Ｒ^５〜Ｒ^１０は、それぞれ独立に水素原子、ハロゲン原子、炭素数１〜１５の飽和及び不飽和アルキル基、又は炭素数１〜１５の飽和及び不飽和アルコキシ基であるか、或いは、Ｒ ^５ 〜Ｒ ^７ 及びＲ ^８ 〜Ｒ ^１０ はそれぞれ独立に、互いに結合を介して異種原子を含んでいても良い芳香族縮合環又は脂肪族環を形成していても良い。）

(In the formula (1), at least one of R ^{1 to} R ⁴ is a substituent containing a polymerizable unsaturated bond having a structure represented by the following formula (2) . Two in one molecule. If there are substituent groups containing a polymerizable unsaturated bond described above, they may be the same or different from each other. in addition, containing a polymerizable unsaturated bond of R ¹ to R ⁴ Those not substituted each independently have a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, an alkoxy group which may have a substituent , an aryloxy group which may have a substituent, or a substituent. A linear, branched or cyclic alkyl group which may be a halogen atom, hydroxyl group, mercapto group, cyano group, silyl group, silanol group, nitro group, unsaturated alkyl ether group, aryl ether Unsaturated alkyl thioether group and .R ⁵ to R ¹⁰ is one or more from the group consisting of aryl thioether group, each independently represent a hydrogen atom, a halogen atom, a saturated or unsaturated alkyl of 1 to 15 carbon atoms group, or a saturated or unsaturated alkoxy groups der Luke 1 to 15 carbon atoms, or ^each R 5 to R ⁷ and ^R 8 ^{to R 10} are independently, also contain heteroatoms via binding to each other (A good aromatic condensed ring or aliphatic ring may be formed.)

（式（２）において、Ｘは、酸素原子、硫黄原子、２級アミノ基、３級アミノ基、又は直接結合である。Ｒ ^１１ は、直鎖、分岐鎖、又は環状、或いはそれらの組み合わせからなる炭素数１〜２０の炭化水素基であって、炭素骨格の途中に、エステル結合、エーテル結合、チオエーテル結合、アミノ結合、アミド結合、ウレタン結合、ウレア結合、チオカルバメート結合、カルボジイミド結合、又は、カーボネート結合を含んでいても良いものであり、Ｒ ^１２ 〜Ｒ ^１４ は、それぞれ独立して水素原子、ハロゲン原子、飽和又は不飽和アルキル基、飽和又は不飽和ハロゲン化アルキル基、又は、飽和又は不飽和ヒドロキシアルキル基であるか、或いは、Ｒ ^１２ とＲ ^１４ は、互いに結合してシクロヘキセン構造を形成していても良い。）
本発明に係る重合性化合物は、ビフェニル骨格の２，２’，６，６’位という特定の部位に重合性不飽和結合を１つ以上有している特定の構造を有するので、ベンゼン骨格を有しながら良好な溶解性を有し、且つ、耐熱性に優れ、加熱時に分解し難くてガスを発生し難い。

(In Formula (2), X is an oxygen atom, a sulfur atom, a secondary amino group, a tertiary amino group, or a direct bond. R ¹¹ is linear, branched, cyclic, or a combination thereof. In the middle of the carbon skeleton, an ester bond, an ether bond, a thioether bond, an amino bond, an amide bond, a urethane bond, a urea bond, a thiocarbamate bond, a carbodiimide bond, or R ^{12 to} R ¹⁴ may each independently contain a hydrogen atom, a halogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated halogenated alkyl group, or a saturated or unsaturated group. (It may be a saturated hydroxyalkyl group, or R ¹² and R ¹⁴ may be bonded to each other to form a cyclohexene structure.)
Since the polymerizable compound according to the present invention has a specific structure having one or more polymerizable unsaturated bonds at specific positions of the 2,2 ′, 6,6 ′ position of the biphenyl skeleton, It has good solubility while having excellent heat resistance, hardly decomposes during heating, and hardly generates gas.

  Since the polymerizable compound according to the present invention has a biphenyl skeleton, the skeleton itself has high heat resistance. Furthermore, the polymerizable compound according to the present invention is characterized in that the π planes of the two benzene rings of the biphenyl skeleton do not have a planar structure due to steric hindrance between the substituents. Therefore, even when the polymerizable compound according to the present invention is a half ester compound, unlike the case where two substituents are fixed on the same plane as in the formula (3), the original compound is heated by heating. Does not decompose into a compound having an acid anhydride and a hydroxyl group. Furthermore, since the polymerizable compound according to the present invention has a bulky steric structure, it is excellent in solubility. In addition, the π-conjugated structure is short due to the twist of the π plane of the benzene ring, and there is an advantage that it is excellent in transparency as compared with a compound having a plurality of other benzene rings connected to each other.

Moreover, in order to solve said 2nd objective, the 2nd aspect of the polymeric compound provided by this invention is one or more polymerizable unsaturated bonds in 1 molecule represented by following formula (1). And at least one of R ^{1 to} R ⁴ in the formula (1) is a hydroxyl group.
In such an embodiment, since the polymerizable compound of the present invention has a carboxyl group in the molecule together with a polymerizable unsaturated bond-containing group, the affinity for an alkaline aqueous solution is improved, and development using an alkaline aqueous solution is performed. Generation of residue at the time can be suppressed. Therefore, it can be suitably used for a pattern forming material that requires a development process, such as a resist material.

In the polymerizable compound of the present invention, in the formula (1), it is preferable to include the polymerizable unsaturated bond of the two or more R ¹ to R ^4. In this case, when the polymerization reaction (curing reaction) is initiated by an external stimulus such as light or heat, the crosslinking reaction proceeds, so the coating film is harder, has a higher glass transition temperature, and has excellent heat resistance. Can be formed.

In the polymerizable compound of the present invention, while said polymerizable unsaturated bond-containing groups for R ¹ and R ^3, other one of R ¹ and R ³ is a hydroxyl group, and, R ² and R ⁴ Is preferably the polymerizable unsaturated bond-containing group and the other of R ² and R ⁴ is a hydroxyl group. In such a case, a polymerizable compound excellent in heat resistance can be obtained while having good alkali developability.

  In the polymerizable compound of the present invention, the molecular weight is preferably from 300 to 3,000 from the viewpoint of ease of handling, curability, solubility and compatibility.

  In the polymerizable compound of the present invention, the 5% weight loss temperature is 200 ° C. or more, and it is difficult to generate decomposition gas from the formed cured film when forming a film using the polymerizable compound. It is preferable from the point.

  The polymer compound according to the present invention is obtained by polymerizing the polymerizable compound according to the present invention.

Next, the resin composition according to the present invention is characterized by containing the polymerizable compound according to the present invention as an essential component.
When the resin composition according to the present invention is applied in a predetermined pattern or molded into a predetermined shape and then externally applied with a stimulus such as heat or light, the polymerizable compound of the present invention causes various polymerization reactions depending on the compounding components. Can cause changes in curing and / or solubility.
The cured product thus obtained exhibits characteristics such as high heat resistance derived from the polymerizable compound of the present invention, transparency, and low outgas.
As a result, the problem of reducing the reliability of the final product is solved. Further, since no outgas is generated, the contamination of the manufacturing equipment is suppressed and the working environment is improved.

Since the resin composition according to the present invention contains the polymerizable compound according to the present invention having a polymerizable unsaturated bond as an essential component, it can be suitably used as a photosensitive resin composition.
When the resin composition according to the present invention is used as a photosensitive resin composition, a radical dimerization reaction or a radical crosslinking reaction is performed depending on a compounding component when light is applied after being applied to a predetermined pattern or formed into a predetermined shape. Etc., various radical reactions can proceed, causing changes in curing and / or solubility. Among these, when the polymerizable compound of the present invention is the second embodiment and contains a carboxyl group in the molecule, the photosensitive resin composition according to the present invention has a pattern-forming material, for example, Due to the effect of increasing the affinity for the alkaline aqueous solution derived from the polymerizable compound of the present invention, which is suitably used as a resist material, the development characteristics of the unexposed area with respect to the alkaline aqueous solution is improved, and development residues and the like are less likely to occur. .

  In the resin composition according to the present invention, a compound having a polymerizable unsaturated bond other than the polymerizable compound according to the present invention, a curing reactive compound having a reactive functional group other than the polymerizable unsaturated bond, light It is preferable to further contain at least one component selected from the group consisting of a polymerization initiator and a polymer compound having a weight average molecular weight of 3000 or more. Thus, the film-forming property in the uncured state of the composition and the physical properties of the coated film after curing can be appropriately adjusted.

  The resin composition according to the present invention is used as a pattern forming material, paint or printing ink, color filter, electronic component, interlayer insulating film, wiring coating film, optical member, optical circuit, optical circuit component, reflection. When used as a material for forming a protective film, hologram, or building material, there is an effect that the product or film has high heat resistance and high stability. In addition, since outgassing during heating is less likely to occur, contamination of the manufacturing apparatus is suppressed and the working environment is improved.

The polymerizable compound of the present invention has high heat resistance, in particular, hardly decomposes during heating and does not easily generate outgas. In addition, because of its bulky three-dimensional structure, it has high transparency, excellent solubility and compatibility.
Among them, in the polymerizable compound of the present invention, in the case of the second embodiment in which at least one of R ^{1 to} R ⁴ in the formula (1) is a hydroxyl group, the affinity for an alkaline aqueous solution is improved, while having high heat resistance, High transparency and excellent solvent solubility.
The polymerizable compound according to the present invention has various problems caused by the decomposition product after the reaction derived from the polymerizable compound having a half ester site, such as a problem of work safety, deterioration of heat resistance and light resistance, Problems such as coloring and fading, peeling of the coating film and occurrence of cracks, which lower the reliability of the final product, and problems of outgassing can be solved.

  In addition, the resin composition containing the polymerizable compound of the present invention as an essential component has high heat resistance and transparency derived from the polymerizable compound, and it is difficult to generate a decomposition product by heating, so it contaminates the manufacturing equipment and work environment. The reliability of the product can be improved. In particular, in the case of the photosensitive resin composition containing the alkali-soluble polymerizable compound of the second aspect as the polymerizable compound of the present invention, due to the effect of increasing the affinity for the alkaline aqueous solution, Development characteristics are improved and development residues are less likely to occur.

The resin composition according to the present invention is cured by irradiation of light, such as a pattern forming material (resist), a coating material, a printing ink, an adhesive, a filler, an electronic material, a molding material, three-dimensional modeling, or the like. It can be used in all known fields and products where changing materials are used, but in particular, paints, printing inks, color filters, electronic components, and interlayer insulation films that require heat resistance and require high reliability. Suitable for forming wiring coating films, optical members, optical circuits, optical circuit components, antireflection films, holograms or building materials.
The printed material, color filter, electronic component, interlayer insulating film, wiring coating film, optical member, optical circuit, optical circuit component, antireflection film, hologram, or building material according to the present invention has high heat resistance, high Since at least a part of the cured product of the stable resin composition is formed, the product or film has high heat resistance and high stability, and thus has a merit of high production yield.

  The present invention is described in detail below. In the present invention, the irradiation light includes not only electromagnetic waves having wavelengths in the visible and invisible regions, but also particle beams such as electron beams, and radiation or ionizing radiation that collectively refers to electromagnetic waves and particle beams. For curing the resin composition, an electromagnetic wave, an electron beam, ionizing radiation or the like having a wavelength of 2 μm or less is mainly used. Moreover, in this specification, (meth) acrylate means that either an acrylate or a methacrylate may be sufficient.

First, the polymerizable compound according to the present invention will be described.
The polymerizable compound provided by the present invention is a polymerizable compound composed of a compound represented by the following formula (1) and having one or more polymerizable unsaturated bonds in one molecule.

（式（１）において、Ｒ^１〜Ｒ^４のうち少なくとも１つは、重合性不飽和結合を含有する置換基である。一分子内に２つ以上の重合性不飽和結合含有基が存在する場合、それらは互いに同一であっても異なっていても良い。また、Ｒ^１〜Ｒ^４のうち重合性不飽和結合含有基でないものはそれぞれ独立に水素原子、ハロゲン原子、水酸基、アミノ基、又は１価の有機基であり、それらは互いに同一であっても異なっていても良い。Ｒ^５〜Ｒ^１０は、それぞれ独立に水素原子、ハロゲン原子、又は１価の有機基であり、それらは互いに同一であっても異なっていても良く、それらが互いに結合を介して環状構造を形成していても良い。）

(In the formula (1), at least one of R ^{1 to} R ⁴ is a substituent containing a polymerizable unsaturated bond. Two or more polymerizable unsaturated bond-containing groups exist in one molecule. In this case, they may be the same as or different from each other, and R ^{1 to} R ⁴ which are not a polymerizable unsaturated bond-containing group are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or A monovalent organic group, which may be the same as or different from each other, and R ^{5 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, They may be the same or different, and they may form a cyclic structure through a bond to each other.)

The polymerizable compound of the present invention can cause a radical reaction by light irradiation, radical polymerization, or a crosslinking reaction by heat. Further, particularly when it is desired to increase the sensitivity to light, the reaction efficiency can be increased by adding a photo radical generator or the like. Furthermore, the crosslinking reaction can be promoted by adding a thermal radical generator.
Further, when the polymerizable compound has two or more polymerizable unsaturated bond-containing groups in one molecule, the polymerizable compound can undergo a crosslinking reaction to form a polymer having a network structure. Here, the term “crosslinking” refers to generation of a crosslinking bond, and the term “crosslinking” refers to a bond formed by bridging any two atoms among molecules composed of atoms bonded in a chain. In this case, the bond may be within the same molecule or between other molecules (Chemical Dictionary Tokyo Chemical Doujin p.1082).

The reason why the polymerizable compound of the present invention represented by the formula (1) exhibits good heat resistance will be described below in comparison with a compound having a similar structure.
As a conventional example of a half ester compound having a plurality of carboxyl groups and polymerizable unsaturated bonds, a reaction for obtaining a half ester compound from pyromellitic dianhydride (PMDA) and 2 equivalents of 2-hydroxyethyl acrylate (HEMA) It is shown as follows.

  At this time, PMDA is a stable 5-membered ring structure in which the acid anhydride moiety is stable and is a planar structure showing a π-conjugated structure throughout the molecule, and the ester bond of the obtained half ester Since the positional relationship and distance of the carboxyl group are fixed, the dealcoholization reaction proceeds by heating or the like and returns to the raw material.

  On the other hand, in the polymerizable compound of the present invention, dealcoholization reaction hardly occurs due to the following reasons. The half ester compound which is one Embodiment of the polymeric compound of this invention below is shown.

The polymerizable compound of the present invention has a biphenyl skeleton in which a carbonyl group is bonded to specific positions such as 2,2 ′, 6,6 ′ positions. In such a half ester structure having a biphenyl skeleton, it is considered that the π planes of the two benzene rings of the biphenyl skeleton are nearly orthogonal due to the ester bond and the steric hindrance of the carboxyl group. Therefore, in the half ester structure contained in the polymerizable compound of the present invention, the distance between the ester bond and the carboxyl group becomes long, and the reaction does not easily proceed. In addition, an acid dianhydride that is considered to be formed by dealcoholization reaction from a half ester is a 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride having a seven-membered ring structure with a large distortion of the acid anhydride moiety. Therefore, it is presumed that the thermal energy exceeding the strain energy is required for the dealcoholization reaction, so that the barrier to the dealcoholization reaction is further increased and the reaction is difficult to proceed.
Therefore, the half ester structure contained in the polymerizable compound of the present invention as described above is very excellent in thermal stability because the half ester is hardly decomposed when heat is applied.
The polymerizable compound of the present invention is one in which substituents having at least a carbonyl group are bonded to the 2-position and 2′-position, 6-position and 6′-position, respectively, of the two benzene rings constituting the biphenyl skeleton. The formation of an ester structure is characterized in that a half ester structure is formed between substituents (for example, an ester bond and a carboxyl group) bonded to different benzene rings. Similarly, even in the case of a compound having a half ester moiety in the biphenyl skeleton, when the position of the substituent forms a half ester structure between substituents bonded to the same benzene ring (for example, 2, 2 ′, 3,3′-biphenyltetracarboxylic acid or 3,3 ′, 4,4′-biphenyltetracarboxylic acid-derived structure), and the pyromellitic dianhydride (PMDA), the dealcoholization reaction proceeds by heating. Therefore, when these are used, the reverse reaction tends to proceed essentially like PMDA, and the thermal decomposition temperature of the compound is lowered.

Such a mechanism makes the polymerizable compound of the present invention difficult to decompose upon heating. Therefore, substituents directly bonded to the 3-position, 4-position and 5-position of the two benzene rings of the biphenyl skeleton (formula ( R ^{5 to} R ¹⁰ ) shown in 1) exhibit the intended function of the present invention regardless of the structure. In particular, it is preferable that they are each independently a hydrogen atom, a halogen atom, or a monovalent organic group because of their availability and cost. Moreover, they may be the same as or different from each other, and they may form a cyclic structure via a bond. The cyclic structure formed by the substituents through a bond includes not only an aliphatic ring structure such as a cyclohexyl group, but also, for example, an aromatic ring bonded to R ⁵ and R ⁶ to form a naphthalene structure. included. Further, the ring structure may be an aromatic condensed ring or an aliphatic ring structure, and may further contain a hetero atom other than a carbon atom as a ring constituent atom.

When it is desired to improve the solubility when the polymerizable compound of the present invention is blended in the resin composition, the substituent introduced into R ^{5 to} R ¹⁰ in the formula (1) is 1 to 15 carbon atoms. It is preferable to select a saturated or unsaturated alkyl group, a saturated or unsaturated alkoxy group having 1 to 15 carbon atoms, a bromo group, a chloro group, a fluoro group, or the like.

In Formula (1), at least one of R ^{1 to} R ⁴ is a substituent containing a polymerizable unsaturated bond. When two or more polymerizable unsaturated bond-containing groups are present in one molecule, they may be the same as or different from each other. Further, among R ^{1 to} R ⁴ , those that are not a polymerizable unsaturated bond-containing group are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, or a monovalent organic group, and they may be the same as each other. It may be different.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. The amino group may be a primary amino group (—NH ₂ ), a secondary amino group, or a tertiary amino group. The secondary amino group is a mono-substituted amino group, for example, methylamino group, ethylamino group, propylamino group, isopropylamino group, tert-butylamino group, anilino group, anisidino group, phenetidino group, toluidino group, xylidino group. , Pyridylamino group, thiazolylamino group, benzylamino group, benzylideneamino group and the like. The tertiary amino group is a disubstituted amino group, which may be cyclic, and is a dimethylamino group, diethylamino group, dibutylamino group, ethylmethylamino group, butylmethylamino group, diamylamino group, dibenzylamino group. , Diphenethylamino group, diphenylamino group, ditolylamino group, dixylamino group, methylphenylamino group, benzylmethylamino group, pyrrolidino group, piperidino group, piperazino group, morpholino group, 1-pyrrolyl group, 1- A pyrazolyl group, 1-imidazolyl group, 1-triazolyl group and the like can be mentioned.

Examples of the monovalent organic group include groups having a hydrocarbon skeleton such as a substituted or unsubstituted saturated or unsaturated aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched or cyclic. The monovalent organic group preferably has about 1 to 20 carbon atoms. These monovalent organic groups may contain bonds and substituents other than hydrocarbon groups such as heteroatoms such as oxygen and nitrogen.
As a bond other than a hydrocarbon group such as a hetero atom contained in a group having a hydrocarbon skeleton, an ether bond, a thioether bond, a carbonyl bond, an ester bond, an amide bond, a urethane bond, a carbonate bond, etc. A halogen atom, a hydroxyl group, a mercapto group, a cyano group, a silyl group, a silanol group, a nitro group, an unsaturated alkyl ether group, an aryl ether group, an unsaturated alkyl thioether group, an aryl thioether group, and the like are exemplified, but not particularly limited.

  Preferred examples of the monovalent organic group include an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a straight chain which may have a substituent, branched or Examples thereof include a cyclic alkyl group.

The polymerizable compound of the present invention preferably has two or more polymerizable unsaturated bonds when it is desired to increase the degree of crosslinking of the polymerizable compound after curing. In this case, ^{one of the} substituents represented by R ^{1 to} R ⁴ may have two or more polymerizable unsaturated bonds, and two or more of the substituents represented by R ^{1 to} R ⁴ may be present. It may be a polymerizable unsaturated bond-containing group. It is preferable that two or more of the substituents represented by R ^{1 to} R ⁴ are polymerizable unsaturated bond-containing groups because the intermolecular crosslinking reaction is easily performed and the effect of improving the crosslinking density is high.

  Here, the polymerizable unsaturated bond in the present invention includes a polymerizable double bond and a polymerizable triple bond. Examples of the functional group constituting the polymerizable double bond include a vinyl group, an isopropenyl group, an allyl group, an allylmethyl group, an acryloyl group, a methacryloyl group, and a 2-trifluoromethylacryloyl group. Examples of the functional group constituting the polymerizable triple bond include ethynyl group and 2-propynyl group. Preferable examples of the polymerizable unsaturated bond include an acryloyl group, a methacryloyl group, and a 2-trifluoromethylacryloyl group.

Among these, when the polymerizable compound of the present invention is used as one component of the photosensitive resin composition, at least one of R ^{1 to} R ⁴ in the formula (1) as the polymerizable unsaturated bond-containing group is: The structure represented by the formula (2) is preferable from the viewpoint of its curability, sensitivity, mechanical properties after curing, and mechanical properties.

（式（２）において、Ｘは、酸素原子、硫黄原子、２級アミノ基、３級アミノ基又は直接結合である。Ｒ^１１は、２価の有機基であり、Ｒ^１２〜Ｒ^１４は、それぞれ独立して水素原子、ハロゲン原子、又は、一価の有機基である。それらは互いに同一であっても異なっていても良く、それらが互いに結合を介して環状構造を形成していても良い。）

(In Formula (2), X is an oxygen atom, a sulfur atom, a secondary amino group, a tertiary amino group, or a direct bond. R ¹¹ is a divalent organic group, and R ^{12 to} R ¹⁴ are: Each independently a hydrogen atom, a halogen atom, or a monovalent organic group, which may be the same as or different from each other, and may form a cyclic structure via a bond to each other; .)

R ¹² , R ¹³ and R ¹⁴ on the polymerizable unsaturated bond contained in the polymerizable compound are each independently a hydrogen atom, a halogen atom or a monovalent organic group. Examples of the monovalent organic group are the same as those described above. R ¹² , R ¹³ and R ¹⁴ on the polymerizable unsaturated bond may be the same as or different from each other, and they may form a cyclic structure via a bond. The ring structure in which substituents are bonded to each other includes not only an aliphatic cyclic structure such as a cyclohexyl group but also a structure in which R ¹² and R ¹⁴ are bonded to form a cyclohexene structure.

R ¹² , R ¹³ and R ¹⁴ are each independently preferably a hydrogen atom, a halogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated halogenated alkyl group, or a saturated or unsaturated hydroxyalkyl group. Particularly preferably, they are each independently a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. In particular, in view of the rate of price or radical reaction, from the viewpoint properties of the final coating, a polymerizable unsaturated bond, R ¹² is a hydrogen atom, a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl Most preferably, R ¹³ and R ¹⁴ are each independently a hydrogen atom or a fluorine atom.

  In the formula (2), X is an oxygen atom, a sulfur atom, a secondary amino group (—NH—), a tertiary amino group (—NR—, where R is a carbon which may have a substituent. A hydrogen group) or a direct bond. From the viewpoint of ease of synthesis and cost, an oxygen atom and a secondary amino group (—NH—) are preferable, and from the viewpoint of cost, an oxygen atom is preferable.

In addition, from the viewpoint of easy availability and ease of synthesis, in the above formula (2), R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms composed of linear, branched, cyclic, or a combination thereof. In the middle of the carbon skeleton, an ester bond, an ether bond, a thioether bond, an amino bond, an amide bond, a urethane bond, a urea bond, a thiocarbamate bond, a carbodiimide bond, or a carbonate bond may be included. preferable.

Specific examples of R ¹¹ include a group represented by — (CH ₂ ) _n — (n is a natural number) such as ethyl, or —CH ₂ CH ₂ — (O—CH ₂ CH ₂ ) _n — (n is a natural number). ), —CH (CH ₃ ) CH ₂ — (O—CH (CH ₃ ) CH ₂ ) _n — (n is a natural number), and the like, but are not limited thereto.

The polymerizable compound largely controls the curability of the resin composition such as the negative photosensitive resin composition and the characteristics after curing. For example, a polymerizable compound having a small molecular weight per polymerizable unsaturated bond has the effect of increasing the hardness of the coating film after curing, and conversely, a polymerizable compound having a large molecular weight per polymerizable unsaturated bond is There exists an effect | action which raises the softness | flexibility of the coating film after hardening. Therefore, the number of polymerizable unsaturated bonds introduced into the polymerizable compound of the present invention so as to express desired physical properties is appropriately determined according to the number thereof, a substituted portion other than the polymerizable unsaturated bond, R ¹¹ and R ¹² to R ¹⁴ and further the structure of R ^{5 to} R ¹⁰ is selected.

In addition, in order to improve the affinity / solubility for the aqueous alkali solution, in the polymerizable compound of the present invention, in the formula (1), at least one of the substituents represented by R ^{1 to} R ⁴ is a hydroxyl group. Preferably, the greater the number, the better the affinity for the alkaline aqueous solution. In such an embodiment, the polymerizable compound of the present invention functions as an alkali-soluble polymerizable compound and can suppress the generation of residues during development using an alkaline aqueous solution. Therefore, it can be suitably used for a pattern forming material that requires a development process, such as a resist material.
In addition, when the substituents represented by R ^{1 to} R ⁴ are hydroxyl groups as described above, a carboxyl group is contained in R ^{1 to} R ⁴ without introducing a carboxyl group directly into the benzene ring of the biphenyl skeleton. As the number of carboxyl groups increases, the affinity for an aqueous alkali solution improves.

The polymerizable unsaturated bond and the number of carboxyl groups contained in the polymerizable compound of the present invention are the alkaline aqueous solution of the object to be provided with the curability of the polymerizable compound, the physical properties after curing, and the affinity / solubility. It is preferable to adjust appropriately depending on the density of the toner and the temperature of the process such as development.
As a suitable example of the polymerizable compound of the present invention, in the formula (1), one of R ¹ and R ³ is a polymerizable unsaturated bond-containing group, and the other ^one of R ¹ and R ³ is a hydroxyl group. In addition, one of R ² and R ⁴ is a polymerizable unsaturated bond-containing group, and the other one of R ² and R ⁴ is a hydroxyl group. In such a case, a polymerizable compound excellent in heat resistance can be obtained while having good alkali developability. The curability is improved, the sensitivity, hardness, strength, adhesion, etc. of the cured film are improved, the pattern edge shape is improved, the residue on the exposed surface due to the development of the substrate is reduced, and the development time is reduced. It becomes possible to obtain a photosensitive resin composition that can be shortened.

The polymerizable compound in the present invention can be synthesized using various known methods. For example, in the case of a structure having two acryloyl groups as functional groups forming a polymerizable unsaturated bond and at least two of R ^{1 to} R ⁴ are hydroxyl groups and two carboxyl groups, 2, 2 ′, 6,6′-biphenyltetracarboxylic dianhydride and 2 equivalents of a compound such as an acrylate having a hydroxyl group such as 2-hydroxyethyl acrylate in γ-butyrolactone dried using pyridine as a catalyst at room temperature It can be obtained quantitatively by stirring.
As another method, 2,2 ′, 6,6′-biphenyltetracarboxylic acid and 2 equivalents of a compound such as acrylate having a hydroxyl group such as 2-hydroxyethyl acrylate are subjected to dehydration condensation using a dehydration catalyst. , 2 ′, 6,6′-biphenyltetracarboxylic acid is converted to an acid chloride using thionyl chloride and the like, reacted with an acrylate having a hydroxyl group, and then the unreacted acid chloride site is deactivated with water to form a carboxyl group. Examples of the method include, but are not limited to.

In addition to acid anhydrides such as 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride and 2,2 ′, 6,6′-biphenyltetracarboxylic acid, as raw materials in the above synthesis method, Derivatives thereof can be used. In order to shift the absorption wavelength of light or adjust the solubility, the above reaction is performed when a substituent is introduced into R ^{5 to} R ¹⁰ of the biphenyl skeleton of the polymerizable compound represented by the formula (1). You may introduce | transduce before, and after making it couple | bond with a polymerizable unsaturated bond and another substituent, you may introduce | transduce.

On the other hand, as a raw material for introducing a polymerizable unsaturated bond, one having a polymerizable unsaturated bond and a functional group capable of being bonded to an acid anhydride is appropriately selected. Examples of the functional group that can be bonded to the acid anhydride include a hydroxyl group, an amino group, an epoxy group, an oxetanyl group, and a thiol group. The substituents R ^{12 to} R ¹⁴ on the polymerizable unsaturated bond may be introduced into the raw material compound in advance, or may be introduced after the polymerizable unsaturated bond and the biphenyl skeleton are bonded.

The method for synthesizing the polymerizable compound of the present invention will be specifically illustrated below, but the present invention is not limited by the following method.
First, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride is added to γ-butyrolactone which has been dried in advance and stirred. 2 mol equivalent of 2-hydroxyethyl acrylate was added to 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, and a catalytic amount of dried pyridine was added. Stir for about an hour. At this time, the reaction solvent to be used is not limited to γ-butyrolactone, and may be any solvent in which the final product is dissolved, and various organic polar solvents are preferably used. Since 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride has a distorted structure, it is highly reactive and easily reacts with water to form carboxylic acid. The yield can be improved by taking care not to contaminate the reaction system.

  As described above, the acid dianhydride used here is not only 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, but also one having a substituent introduced beforehand depending on the purpose. May be.

Further, the hydroxyl group-containing compound used here is not limited to 2-hydroxyethyl acrylate, and various hydroxyl group-containing compounds can be used depending on the purpose. For example, a compound containing a polymerizable unsaturated bond and a hydroxyl group as exemplified below may be used, but is not limited thereto: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta Hydroxyalkyl (meth) acrylates such as) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 2-hydroxy-3-phenylpropyl acrylate, etc. Diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate DOO, polypropylene glycol mono (meth) acrylates, such as polyoxytetramethylene glycol mono (meth) acrylate (poly) oxy-C _2-4 alkylene glycol mono (meth) acrylate; propargyl alcohol. A compound containing a hydroxyl group that does not contain a polymerizable unsaturated bond may be used in combination as appropriate. Examples of such a compound containing a hydroxyl group include methanol, ethanol, isopropanol, cyclohexanol, phenol and the like.

In this manner, the solvent of the reaction liquid stirred for several hours is removed by distilling or throwing it into water or the like, and the target product is taken out. By performing a treatment such as recrystallization, the polymerizable compound of the present invention can be obtained. The purification method is not limited to recrystallization, and any known method such as sublimation purification or column chromatography can be used, but recrystallization is preferable from the viewpoint of cost.

In addition, the compound in which all four substituents represented by R ^{1 to} R ⁴ in the formula (1) are polymerizable unsaturated bond-containing groups has, for example, a carboxyl group having a half ester structure obtained as described above. Further, it can be obtained by acid chloride using thionyl chloride or the like and then reacting with a compound containing a polymerizable unsaturated bond and a hydroxyl group in the presence of an amine.

  Since the polymerizable compound according to the present invention has a bulky steric structure, it has excellent solubility and transparency despite having two aromatic rings. Furthermore, when a stimulus such as light or heat is applied, the polymerization reaction at the site of the polymerizable unsaturated bond proceeds. The polymerizable compound of the present invention and the cured product after the polymerization reaction are excellent in heat resistance because the half ester site is not easily decomposed into an acid anhydride site and alcohol by heating. In addition, when the polymerizable compound of the present invention has two or more polymerizable unsaturated bonds in one molecule, a crosslinking reaction proceeds and a material with improved heat resistance can be obtained.

  The molecular weight of the polymerizable compound of the present invention is preferably from 300 to 3000 from the viewpoints of ease of handling, curability, solubility and compatibility. If it is smaller than 300, the biphenyl skeleton cannot be contained in the molecule, and the object of the present invention to improve heat resistance cannot be achieved. When it is larger than 3000, the number of polymerizable substituents and the number of carboxyl groups per molecule are reduced, and functions such as curability and affinity for an aqueous alkali solution are hardly exhibited. In addition, the said molecular weight is a weight average molecular weight in the case where the polymeric compound of this invention has a repeating unit, Comprising: The value of polystyrene conversion by gel permeation chromatography (GPC) is said.

When the polymerizable compound of the present invention is used as a component of a photosensitive resin composition, the emission wavelength of a high-pressure mercury lamp generally used for exposure of the photosensitive resin in order to increase the sensitivity of the photosensitive resin composition. Thus, it is preferable that the three wavelengths of 365 nm (i-line), 405 nm (h-line), and 436 nm (g-line) having relatively high intensity have as little absorption as possible. Specifically, it is preferable that at least one of the three wavelengths does not have absorption. In this case, having no absorption means that the molar extinction coefficient measured by an acetonitrile solution or a methanol solution having a concentration of 1.0 × 10 ⁻³ mol / L or less of the polymerizable compound is 100 or less.
Among these, it is particularly preferable that the absorption has no absorption at a wavelength of 365 nm (i-line) having the highest intensity.

From the viewpoint of heat resistance, the 5% weight reduction temperature of the polymerizable compound according to the present invention is preferably 200 ° C. or higher, and more preferably 220 ° C. or higher.
Here, the 5% weight reduction temperature is the time when the weight of the sample is reduced by 5% from the initial weight when the weight reduction is measured using a thermogravimetric analyzer in the same manner as in the examples of the present invention described later. (In other words, the temperature is 95% of the initial sample weight).

  The polymerizable compound according to the present invention preferably has a total light transmittance (JIS K7105) of 90% or more, more preferably 95% or more when the thickness of the cured film is 10 μm.

The polymerizable compound preferably has high solubility when blended in the resin composition from the viewpoint of improving coating suitability, transparency after curing, sensitivity during exposure, and the like.
In view of coating suitability at the time of coating, the polymerizable compound is particularly preferably highly soluble in a solvent. Specifically, it is preferable that the solubility of the polymerizable compound in the solvent to be used, particularly a general-purpose solvent described later, is 0.1% by weight or more.

Since the two benzene rings of the biphenyl skeleton do not have a planar structure, the polymerizable compound of the present invention has a bulky steric structure, solubility in a solvent, and other polymerizations used in the resin composition. Good compatibility with functional compounds and polymer compounds. However, when it is necessary to further improve the solubility or compatibility of the polymerizable compound, it can be improved by introducing a substituent into the biphenyl skeleton of the polymerizable compound. For example, as described above, the substituents R ^{5 to} R ¹⁰ on the biphenyl skeleton include a saturated or unsaturated alkyl group having 1 to 15 carbon atoms, a saturated or unsaturated alkoxy group having 1 to 15 carbon atoms, a bromo group, It is preferable to introduce a chloro group, a fluoro group or the like as appropriate. In addition, R ^{1 to} R ⁴ in the above formula (1), and further, the structure of R ^{11 in} the above formula (2) may be changed, or the target compound to be improved in solubility and compatibility in this portion may be used. The solubility or compatibility of the polymerizable compound can also be improved by introducing a substituent having a structure similar to that of the polymerizable compound.
The substituents introduced into these sites or the structural changes to be applied are variously selected depending on the solvent to be dissolved or other components to be compatible. For example, when a carboxyl group is selected as a substituent, it becomes easy to dissolve in water or an organic polar solvent, and when an ester is introduced, the solubility in a solvent or compound having an ester bond is improved.

On the other hand, the polymer compound according to the present invention is a polymer compound obtained by polymerizing the polymerizable compound according to the present invention. As a means for polymerization, light irradiation, heating, a catalyst or the like is appropriately selected and used.
Since the polymer compound according to the present invention is obtained by polymerizing the polymerizable compound according to the present invention, since the transparency is high and the thermal decomposition temperature is high as described above, the coating film is deteriorated. There is no problem of generation of outgas, and there are no problems such as deterioration of light resistance, coloring or fading, peeling of a coating film or generation of cracks. Therefore, there is an advantage that the reliability of the final product, for example, an interlayer insulating film for electronic parts, a solder resist, and a color filter pixel forming resist can be improved.

Next, the resin composition according to the present invention will be described.
The resin composition according to the present invention contains the polymerizable compound according to the present invention as an essential component, and if necessary, a compound having a polymerizable unsaturated bond other than the polymerizable compound according to the present invention. In addition to photopolymerization initiators such as photopolymerization initiators such as photopolymerization initiators such as photopolymerization initiators, sensitizers, and the like, various additives Etc., and may contain other components.

  The resin composition according to the present invention is applied to a predetermined pattern or molded into a predetermined shape, and then given a stimulus such as heat or light irradiation, thereby the polymerizable unsaturated bond of the polymerizable compound according to the present invention. The reaction proceeds to cause curing and / or solubility changes. Since the resin composition according to the present invention contains the polymerizable compound according to the present invention as an essential component, the heat resistance and transparency are good, and it is difficult to generate a decomposition product even when heated after the reaction is completed. Since no outgas is generated, there is a merit that a highly reliable cured film can be obtained.

  In particular, when the polymerizable unsaturated bond of the polymerizable compound according to the present invention contained is one that reacts by light irradiation like a polymerizable double bond, the resin composition according to the present invention is photosensitive. It can be used as a resin composition. In this case, it is preferable to contain a polymerization initiator such as a photo radical generator. When the photosensitive resin composition according to the present invention is irradiated with light after being applied or formed into a predetermined shape, a photoradical reaction is started in the light irradiation part, and a radical dimerization reaction or radical property is caused by a blending component. Various radical reactions such as cross-linking reactions proceed to cause changes in curing and / or solubility. Therefore, when light is irradiated in a pattern using an appropriate mask or the like, only the irradiated portion is cured, and a desired pattern can be formed by eluting unexposed portions. Furthermore, when the polymerizable compound according to the present invention to be used has a carboxyl group and is an alkali-soluble polymerizable compound, the photosensitive resin composition according to the present invention has only an unexposed portion after light irradiation in a pattern. A desired pattern can be formed by alkali development.

  In order for the resin composition according to the present invention to exhibit a sufficient effect, the polymerizable compound according to the present invention is 0.1% by weight or more of the total solid content of the resin composition. This is preferable from the viewpoint of preventing the curing rate of the resin composition from slowing down and the strength and heat resistance of the coating film from decreasing. The polymerizable compound according to the present invention is more preferably 1% by weight or more of the total solid content of the resin composition from the viewpoints of sensitivity and physical properties of the coating film. In addition, solid content of a resin composition is all components other than a solvent, and a liquid monomer component is also contained in solid content.

  In particular, in the resin composition according to the present invention, since the compatibility of the polymerizable compound according to the present invention with respect to other compounding components is high due to its three-dimensional structure, the polymerizable compound according to the present invention is benzene. In spite of having a plurality of skeletons, the blending ratio can be increased, for example, the solid content concentration can be 30% by weight or more. Thus, when making a mixture ratio high, while improving the sensitivity of a photoradical reaction, a crosslinking density can be improved and the heat resistance of a cured film can be improved.

Next, other components contained in the resin composition according to the present invention will be described.
The resin composition according to the present invention may further contain a compound having a polymerizable unsaturated bond other than the polymerizable compound according to the present invention. A compound having a polymerizable double bond (ethylenic double bond) has been widely used as a radically polymerizable curing reactive compound, and has a wide range of applications. It is suitably used as a constituent component.
The compound having a polymerizable unsaturated bond other than the polymerizable compound according to the present invention includes a compound having one or more polymerizable unsaturated bonds, and other functionalities together with at least one polymerizable unsaturated bond. A compound having a group can be used. Examples include aromatic vinyl compounds such as amide monomers, (meth) acrylate monomers, urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, epoxy (meth) acrylates, hydroxyl-containing (meth) acrylates, and styrene. Can do. In addition, a polymer compound having a polymerizable unsaturated bond at the terminal, side chain, or the like may be used.

Examples of amide monomers include amide compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, and acryloylmorpholine.
Examples of (meth) acrylate monomers include imide acrylates such as hexahydrophthalimidoethyl acrylate and succinimide ethyl acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenylpropyl Hydroxyalkyl (meth) acrylates such as acrylates; acrylates of alkylene oxide adducts of phenols such as phenoxyethyl (meth) acrylates and their halogen nucleus substitutions; mono- or di (meth) acrylates of ethylene glycol, methoxyethylene glycols Mono (meth) acrylate, tetraethylene glycol mono or di (meth) acrylate, tripropylene glycol mono or di (meth) acrylate, etc. Mono- or di (meth) acrylates of glycols; polyols such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate, dipentaerythritol hexaacrylate and alkylene oxides thereof ( Examples include meth) acrylic ester, isocyanuric acid EO-modified di- or tri (meth) acrylate.

Examples of the urethane (meth) acrylate oligomer include a reaction product obtained by further reacting a reaction product of a polyol and an organic polyisocyanate with a hydroxyl group-containing (meth) acrylate as described above.
Here, examples of the polyol include a low molecular weight polyol, polyethylene glycol, and polyester polyol, and examples of the low molecular weight polyol include ethylene glycol, propylene glycol, cyclohexanedimethanol, and 3-methyl-1,5-pentanediol. Examples of the polyether polyol include polyethylene glycol and polypropylene glycol. Examples of the polyester polyol include these low molecular weight polyols and / or polyether polyols, adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid. And a reaction product with an acid component such as a dibasic acid or an anhydride thereof.

  Examples of the organic polyisocyanate to be reacted with the polyol include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

Examples of the polyester (meth) acrylate oligomer include a dehydration condensate of a polyester polyol and (meth) acrylic acid as described in the urethane (meth) acrylate.
Epoxy (meth) acrylate is an addition reaction of unsaturated carboxylic acid such as (meth) acrylic acid to epoxy resin. Epoxy (meth) acrylate of bisphenol A type epoxy resin, phenol or cresol novolac type epoxy resin And (meth) acrylic acid addition reactant of diglycidyl ether of polyether.

  Examples of the polymer compound having a polymerizable unsaturated bond at the terminal, side chain, etc. include a polymer obtained by reacting a copolymer of styrene-maleic anhydride with 2-hydroxyethyl acrylate, polyvinyl alcohol and anhydrous A compound obtained from the reaction of maleic acid, a reaction product of polyvinyl alcohol or poly-2-hydroxyethyl acrylate and acryloyloxyethyl isocyanate can be mentioned, but the invention is not limited thereto.

  The compound having a polymerizable unsaturated bond other than the polymerizable compound according to the present invention preferably has 2 or more, particularly 3 or more polymerizable unsaturated bonds from the viewpoint of three-dimensional crosslinking.

  Further, when the resin composition according to the present invention is used as a resist for forming a pattern by exposure in applications such as an electronic member and a color filter, the present invention is used to improve the alkali developability of the entire resin composition. As the compound having a polymerizable unsaturated bond other than the polymerizable compound according to the above, a compound having an alkali-soluble or hydrophilic functional group such as a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a hydroxyl group may be used. .

  In addition, since the compound having a polymerizable unsaturated bond other than the polymerizable compound according to the present invention does not hinder the sensitivity of the resin composition to the irradiation light, the irradiation wavelength and the absorption wavelength of the non-degradable photoradical generation site are It is preferable that there is no absorption in the overlapping wavelength region.

In the photosensitive resin composition of the present invention, in order to adjust the film-forming property in the uncured state of the composition and the physical properties of the coated film after curing, the binder resin has reactivity other than the polymerizable unsaturated bond. A curing reactive compound having a functional group or a polymer compound may be blended.
As the binder resin, any known polymer compound or a curing reactive compound having a reactive functional group other than the polymerizable unsaturated bond can be used according to the use of the resin composition. As the polymer compound, any of a non-reactive polymer and a polymer having a polymerizable unsaturated bond or other reactive functional group may be used. The polymer compound used as the binder component preferably has a weight average molecular weight of 3000 or more, and if the molecular weight is too large, the solubility and processing characteristics are deteriorated. It is preferable that it is below 000,000. Here, the weight average molecular weight in the present invention refers to a value in terms of polystyrene by gel permeation chromatography (GPC).

  Examples of the polymer compound other than the compound having a polymerizable unsaturated bond and / or a curing reactive compound having a reactive functional group other than the polymerizable unsaturated bond include tolylene diisocyanate and 4,4′-diphenylmethane diisocyanate. , 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and other organic polyisocyanates; vinyl acetate, vinyl chloride, acrylic acid esters, methacrylic acid esters, and other polymers and copolymers; polystyrene Styrenic resins such as acetal resins such as formal resins and butyral resins; silicone resins; phenoxy resins; epoxy resins typified by bisphenol A type epoxy resins; urethane resins such as polyurethane; Polyketone resin; Polyether resin; Polyphenylene ether resin; Polybenzoxazole resin; Cyclic polyolefin resin; Polycarbonate resin; Polyester resin; Polyarylate resin; Polystyrene resin; Novolak resin; And alicyclic polymers such as polybenzimidazole and polynorbornene; all known polymer compounds such as siloxane polymers or curing reactive compounds.

As described above, the compound having a polymerizable unsaturated bond other than the polymerizable compound according to the present invention, the polymer compound, and the curing reactive compound having a reactive functional group other than the polymerizable unsaturated bond are each independent. Or may be used in combination of two or more.
Curing having a reactive functional group other than a compound having a polymerizable unsaturated bond other than a polymerizable compound, a polymer compound, and / or a compound having a polymerizable unsaturated bond, contained in the resin composition according to the present invention. The content of the reactive compound is not particularly limited and is appropriately adjusted for necessary physical properties according to the respective uses.

  Further, when the resin composition according to the present invention contains a non-reactive polymer compound, the non-reactive polymer compound is 1% by weight or more and 97% by weight of the solid content of the entire resin composition depending on the application. It is preferable to contain so that it may become the following. When the amount of the non-reactive polymer compound is more than 97% by weight, the curability by light tends to be lowered.

  In addition, when the resin composition according to the present invention is used in combination with a compound having a polymerizable unsaturated bond and a curing reactive compound having another reactive functional group, the type and amount of the curing reactive compound to be combined. The amount of the compound having a polymerizable unsaturated bond is appropriately adjusted according to the conditions.

When the resin composition of the present invention is cured by light, other photoradical generators may be used as necessary in order to promote the radical reaction.
Examples of the photo radical generator include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 Acetophenones such as phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiary-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethyl Thioxanthone such as luthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; 2,4,6-trimethylbenzoyldiphenylphosphine oxide Monoacylphosphine oxide or bisacylphosphine oxide; benzophenones such as benzophenone; and xanthones.

  These photo radical generators can be used alone or in combination with a photopolymerization initiation accelerator such as benzoic acid or amine. A preferable blending ratio of these photo radical generators is 0.1% by weight or more and 35% by weight or less, more preferably 1% by weight or more and 10% by weight or less based on the entire solid content of the resin composition.

In order to impart processing characteristics and various functionalities to the resin composition according to the present invention, various organic or inorganic low-molecular or high-molecular compounds may be blended. For example, dyes, surfactants, leveling agents, plasticizers, fine particles, sensitizers, and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate, and the functions or forms include pigments, fillers, fibers, and the like.
The blending ratio of these optional components is preferably in the range of 0.1 wt% to 95 wt% with respect to the entire solid content of the resin composition. When the amount is less than 0.1% by weight, the effect of adding the additive is hardly exhibited, and when the amount exceeds 95% by weight, the characteristics of the resin composition according to the present invention are hardly reflected in the final product.

  When a large amount of a component that absorbs irradiation light is blended in the resin composition, light does not sufficiently reach the polymerizable compound according to the present invention, and sensitivity is lowered. Therefore, from the point of emphasizing the sensitivity of the resin composition, the polymerization according to the present invention in the wavelength region where the emission wavelength of the irradiation light source and the absorption wavelength of the polymerizable compound according to the present invention mixed in the resin composition overlap. It is preferable to appropriately select the components used in the resin composition by adjusting the transmittance of all the components other than the functional compound so as to be 20% or more.

  Moreover, you may dilute the resin composition which concerns on this invention to a suitable density | concentration using a solvent. As the solvent, various general-purpose solvents such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and the like; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Glycol monoethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether (so-called cellosolves); ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone; acetic acid Ethyl, butyl acetate, n acetate Propyl, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetate esters of the above glycol monoethers (for example, methyl cellosolve acetate, ethyl cellosolve acetate), methoxypropyl acetate, ethoxypropyl acetate, dimethyl oxalate, lactic acid Esters such as methyl and ethyl lactate; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin; methylene chloride, 1,1-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, Halogenated hydrocarbons such as 1-chlorobutane, 1-chloropentane, chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene; N, N-dimethylform Amides such as amide, N, N-dimethylacetamide; pyrrolidones such as N-methylpyrrolidone; lactones such as γ-butyrolactone; sulfoxides such as dimethyl sulfoxide; and other organic polar solvents, and the like. , Aromatic hydrocarbons such as benzene, toluene and xylene, and other organic nonpolar solvents. As the reactive diluent, a compound having a reactive functional group in the structure, such as an ethylenically unsaturated compound that is liquid at room temperature, may be used as a solvent. These solvents are used alone or in combination. These solvents may be used after filtering impurities by various known methods such as a filter having a pore diameter of about 0.05 μm to 0.2 μm.

  Moreover, even if the resin composition is transparently dissolved using a solvent, if the compatibility of the solids contained in the resin composition is low, if the solvent evaporates during coating, A precipitate is formed, and sufficient transparency cannot be obtained. Therefore, when a highly transparent coating film or molded body is required, such as an optical member, a polymerizable compound having high compatibility with other solid components in the resin composition may be appropriately selected and used. preferable. When high transparency is required, the total light transmittance (JIS K7105) is preferably 90% or more and 95% or more when the thickness of the coating film formed by curing the resin composition is 10 μm. More preferably.

  The resin composition according to the present invention includes the polymerizable compound according to the present invention which is an essential component, a compound having a polymerizable unsaturated bond other than the polymerizable compound as necessary, and a compound having the polymerizable unsaturated bond. It can be prepared by mixing other optional components such as a curing reactive compound, a high molecular weight binder component and the like according to the case and application.

  The resin composition according to the present invention obtained in this way is a pattern forming material (resist), a coating material, a printing ink, an adhesive, a filler, an electronic material, a molding material, three-dimensional modeling, etc. by light irradiation or heating. It can be used in all known fields and products in which a material that is cured or changes in solubility is used. In particular, paints, printing inks, color filters, electronic components, interlayer insulation films, wiring coating films, optical members, optical circuits, optical circuit components, antireflection films, which require heat resistance and require high reliability, Suitable for forming holograms or building materials.

For example, in the case of a color filter, a pixel portion, a light shielding portion (black matrix) provided at the boundary of the pixel portion, a protective film, and a spacer for maintaining a cell gap are formed from a cured product of the photosensitive resin composition. can do.
In the case of an electronic component, for example, an underfill agent and a sealant for a semiconductor device can be exemplified.
The interlayer insulation film is a cured product of the above resin composition, such as an interlayer insulation film for build-up substrates that require heat resistance and insulation reliability, an interlayer insulation film for fuel cells, and an insulation coating for automobile parts and household appliances. Can be formed.

Examples of the wiring protective film include a solder resist that is a wiring protective layer on the surface of the printed wiring board, and a surface coating of the electric wire.
In the case of an optical member, examples thereof include overcoats of various optical lenses, optical circuit components such as antireflection films, optical waveguides, and branching devices, relief-type and volume-type holograms, and the like.
In the case of building materials, wallpaper materials, wall materials, floor materials, and other skin materials with low volatile components, adhesive / adhesive materials, inks, and the like can be exemplified.

  The printed matter, color filter, electronic component, interlayer insulating film, wiring coating film, optical member, optical circuit, optical circuit component, antireflection film, hologram, or building material according to the present invention has high heat resistance and high stability. Since at least a part of the cured resin composition is formed, it has high heat resistance and high stability, and therefore has a merit of high production yield.

1. Synthesis of polymerizable compound (Example 1)
<Synthesis of Polymerizable Compound 1>
Into a 100 mL (liter) flask, 2.94 g (10 mmol) of 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, 10 ml of dried γ-butyrolactone and a catalytic amount of pyridine were added and stirred. did. Thereto was added 2.86 g (22 mmol) of 2-hydroxyethyl acrylate, and the mixture was stirred at room temperature for 16 hours under a nitrogen stream. Then, the reaction solution was separated with 0.1 N hydrochloric acid and chloroform, and the chloroform layer was sulfated. After drying with magnesium, chloroform was distilled off to obtain 4.5 g of a viscous liquid substance (mixture of isomers as described below) (polymerizable compound 1).
¹ H NMR (400 MHz, DMSO-d6) δ (ppm): 12.55 (br, 2H COO H ), 7.97 (m, 4H Ar), 7.52 (m, 2H Ar), 5.93 ( _{d, 2H H -CH = CCH 3} -), 5.65 (d, 2H H -CH = CCH 3 -) 4.11 (t, 4H -O-C H 2 -CH 2 O-) 3.94 ( _{t, 4H -OCH 2 -C H 2} -O -), 1.81 (s, 6H -C H 3).

(Example 2)
<Preparation of photosensitive resin composition 1>
A photosensitive resin composition 1 was prepared by dissolving 475 mg of the polymerizable compound 1 and 25 mg of a photopolymerization initiator Irgacure OXE-02 (manufactured by Ciba Specialty Chemicals) in 2 mL of γ-butyrolactone.

(Comparative Example 1)
<Synthesis of Comparative Polymerizable Compound 1>
In a 100 mL (liter) type flask, 4.36 g (20 mmol) of pyromellitic dianhydride, 15 ml of dried γ-butyrolactone and a catalytic amount of pyridine were added and stirred. Thereto was added 5.35 ml (44 mmol, 5.73 g) of 2-hydroxyethyl acrylate, and the mixture was stirred at room temperature for 16 hours under a nitrogen stream. Then, an appropriate amount of sodium chloride was added to 2 L of 0.1 N hydrochloric acid. The precipitate was filtered and dried to obtain 9.5 g of a white solid (mixture of isomers as described below). (Comparative polymerizable compound 1)

2. Evaluation (1) Solubility Evaluation 100 mg of each of the polymerizable compound 1 and the comparative polymerizable compound 1 was added to 200 μl of γ-butyrolactone, and the ultrasonic wave was irradiated for 2 hours with an ultrasonic cleaner to evaluate the solubility. Although the polymerizable compound 1 was completely dissolved, a white precipitate was observed in the comparative polymerizable compound 1.

(2) Pyrolysis temperature measurement Using a differential type differential thermal balance (product name: TG8120, manufactured by Rigaku Corporation), a comparative polymerization with polymerizable compound 1 at a temperature increase rate of 10 ° C./min in a nitrogen atmosphere. The 5% weight loss temperature of the active compound 1 was measured. The results are shown in the following table.

(3) Pattern formation evaluation The photosensitive resin composition 1 (Example 2) was spin-coated on a glass plate so as to have a final film thickness of 2 μm, and dried on a hot plate at 80 ° C. for 10 minutes. Then, 100 mJ UV irradiation was performed by a manual exposure apparatus (manufactured by Dainippon Screen Co., Ltd., MA-1200) through a photomask having a predetermined pattern in terms of h-ray, and a tetramethylammonium hydroxide 2.38% solution. Soaked in. As a result, a pattern was obtained in which the exposed portion remained undissolved in the developer. No residue or the like was found in the elution part.
From this result, it became clear that the photosensitive resin composition 1 of the present invention can form a good pattern.

Claims (11)

A polymerizable compound comprising a compound represented by the following formula (1) having one or more polymerizable unsaturated bonds in one molecule.

(In the formula (1), at least one of R ^{1 to} R ⁴ is a substituent containing a polymerizable unsaturated bond having a structure represented by the following formula (2) . Two in one molecule. If there are substituent groups containing a polymerizable unsaturated bond described above, they may be the same or different from each other. in addition, containing a polymerizable unsaturated bond of R ¹ to R ⁴ Those not substituted each independently have a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, an alkoxy group which may have a substituent , an aryloxy group which may have a substituent, or a substituent. A linear, branched or cyclic alkyl group which may be a halogen atom, hydroxyl group, mercapto group, cyano group, silyl group, silanol group, nitro group, unsaturated alkyl ether group, aryl ether Unsaturated alkyl thioether group and .R ⁵ to R ¹⁰ is one or more from the group consisting of aryl thioether group, each independently represent a hydrogen atom, a halogen atom, a saturated or unsaturated alkyl of 1 to 15 carbon atoms group, or a saturated or unsaturated alkoxy groups der Luke 1 to 15 carbon atoms, or ^each R 5 to R ⁷ and ^R 8 ^{to R 10} are independently, also contain heteroatoms via binding to each other (A good aromatic condensed ring or aliphatic ring may be formed.)

(In Formula (2), X is an oxygen atom, a sulfur atom, a secondary amino group, a tertiary amino group, or a direct bond. R ¹¹ is linear, branched, cyclic, or a combination thereof. In the middle of the carbon skeleton, an ester bond, an ether bond, a thioether bond, an amino bond, an amide bond, a urethane bond, a urea bond, a thiocarbamate bond, a carbodiimide bond, or R ^{12 to} R ¹⁴ may each independently contain a hydrogen atom, a halogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated halogenated alkyl group, or a saturated or unsaturated group. (It may be a saturated hydroxyalkyl group, or R ¹² and R ¹⁴ may be bonded to each other to form a cyclohexene structure.) The polymerizable compound according to claim 1, wherein in the formula (1), at least one of R ^{1 to} R ⁴ is a hydroxyl group. In the above formula (1), R ¹ to R ⁴ in include the polymerizable unsaturated bond of 2 or more, polymerizable compound according to claim 1 or 2. In the formula (1), with substituents one of ^{R 1} and ^{R 3} contains a polymerizable unsaturated bond, other one of ^{R 1} and ^{R 3} is a hydroxyl group, and, for ^{R 2} and ^{R 4} The polymerizable compound according to claim 1, wherein one is a substituent containing the polymerizable unsaturated bond, and the other of R ² and R ⁴ is a hydroxyl group. Molecular weight is 300 to 3,000, a polymerizable compound according to any one of claims 1 to 4. 5% weight loss temperature is 200 ° C. or more, polymerizable compound according to any one of claims 1 to 5. Claims 1 to polymerizable compound is polymerized resultant polymer compound according to any one of 6. A resin composition comprising the polymerizable compound according to any one of claims 1 to 6 as an essential component. The resin composition according to claim 8 , which is a photosensitive resin composition. A compound having a polymerizable unsaturated bond other than the polymerizable compound according to any one of claims 1 to 6 , a curing reactive compound having a reactive functional group other than the polymerizable unsaturated bond, a photopolymerization initiator, The resin composition according to claim 8 or 9 , further comprising at least one component selected from the group consisting of a polymer compound having a weight average molecular weight of 3000 or more. The resin composition according to claim 9 or 10 , which is used as a pattern forming material.