KR20070038902A - Curable resin composition, process for forming a cured film, and cured film - Google Patents

Abstract

The present invention is polymerized by living radical polymerization in the presence of a specific thiocarbonylthio compound, and the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (Mw / Mn) Is 1.7 or less, and further relates to a curable resin composition containing a polymer having a carboxyl group or an oxiranyl group or an oxetanyl group.

Thiocarbonylthio compound, living radical polymerization, curable resin composition

Description

Curable Resin Composition, Process for Forming Cured Film and Cured Film {Curable Resin Composition, Process for Forming a Cured Film, and Cured Film}

1 is a schematic diagram illustrating a cross-sectional shape of a spacer.

2 is a schematic diagram showing the cross-sectional shape of a microlens, (a) is a semi-convex lens shape, and (b) is a substantially trapezoidal shape.

[Document 1] Japanese Unexamined Patent Publication No. 2001-261761

[Document 2] Japanese Unexamined Patent Publication No. 2001-354822

[Document 3] Japanese Unexamined Patent Publication No. 2001-343743

[Document 4] Japanese Unexamined Patent Publication No. 6-18702

[Patent 5] Japanese Unexamined Patent Publication No. 6-136239

[Patent 6] Japanese Unexamined Patent Publication No. 5-78453

The present invention relates to a curable resin composition containing a specific resin, a method of forming a cured film that is a spacer, an interlayer insulating film, a microlens or a protective film using the same, and a cured film.

<Conventional technology regarding spacers>

Conventionally, in the liquid crystal display device, spacer particles such as glass beads and plastic beads having a predetermined particle diameter are used to maintain a constant gap between two transparent substrates, but these spacer particles are randomly formed on a transparent substrate such as a glass substrate. Since there is a problem that the spacer particles are present in the pixel formation region, the particles may be taken out or the incident light may be scattered so that the contrast of the liquid crystal display device may be lowered.

Therefore, in order to solve these problems, the method of forming a spacer by photolithography has been employ | adopted (for example, refer Unexamined-Japanese-Patent No. 2001-261761.). In this method, the radiation-sensitive resin composition is applied onto a substrate, and then irradiated with ultraviolet rays through a predetermined mask to be developed to form spacers in the shape of dots or stripes, and the spacers can be formed only at predetermined places other than the pixel formation region. The problem as described above is basically solved.

However, in the conventional radiation sensitive resin composition, it is concerned that the sublimation which arises at the time of baking for forming a spacer contaminates a process line or a device, and the radiation sensitive resin composition which reduced generation | occurrence | production of a sublimation was desired.

Conventional Techniques Regarding Interlayer Insulators and Microlenses

Electronic components such as thin film transistors (hereinafter referred to as "TFT") type liquid crystal display elements, magnetic head elements, integrated circuit elements, and solid-state image pickup elements are generally provided with an interlayer insulating film to insulate between layers arranged in layers. have. As the material for forming the interlayer insulating film, a radiation-sensitive resin composition has been widely used because it is preferable that the number of steps for obtaining the required pattern shape is small and the flatness is sufficient (Japanese Patent Laid-Open No. 2001-354822 and Japanese Patent Laid-Open) See Publication 2001-343743.).

Among the electronic components, for example, a TFT type liquid crystal display element is manufactured through a process of forming a transparent electrode film on the interlayer insulating film and forming a liquid crystal alignment film thereon, so that the interlayer insulating film is a high temperature condition in the process of forming the transparent electrode film. Sufficient resistance to these is required because it is exposed to the exfoliating solution of the resist which is exposed to or used to form the electrode. In addition, recent TFT-type liquid crystal display devices tend to have large screens, high brightness, high precision, high-speed response, and thinning, and have high sensitivity as a composition for forming an interlayer insulating film used therein. In terms of transmittance and the like, a higher performance and a higher performance have been required.

On the other hand, a microlens having a lens diameter of about 3 to 100 μm or a microlens in which a plurality of such microlenses are regularly arranged as an imaging optical system of an on-chip color filter such as a facsimile, an electronic copier, a solid-state imaging device or an optical system material of an optical fiber connector Array is being used.

The formation of a microlens or microlens array is performed by forming a patterned film corresponding to a desired lens shape and then melting it by heat treatment to use it as a lens, or by dry etching using the melted lens pattern as a mask. The method of transferring a lens shape to this is known. The radiation sensitive resin composition is widely used for formation of the said lens pattern (refer Unexamined-Japanese-Patent No. 6-18702 and Unexamined-Japanese-Patent No. 6-136239).

In order to remove various insulating films on the bonding pad, which is a wiring forming portion, the device on which the microlens or the microlens array is formed is coated with a planarization film and an etching resist film, and then exposed and developed using a desired mask to bond the pad. The etching resist of the portion is removed, and then, the planarization film or various insulating films are removed by etching to expose the bonding pad portion. Therefore, the microlens or the microlens array requires solvent resistance and heat resistance in the coating film forming step and the etching step of the planarization film and the etching resist.

The radiation-sensitive resin composition used to form such a microlens is not only highly sensitive but also has a desired radius of curvature, and is required to have high heat resistance, high transmittance, and the like.

In the above interlayer insulating film or microlens, if the developing time is excessively shorter than the optimum time in the developing step in forming them, the developer may penetrate between the pattern and the substrate, and peeling may easily occur. There was a problem in process control because it was necessary to control the developing time strictly.

Thus, when forming an interlayer insulation film and a microlens from a radiation sensitive resin composition, high sensitivity is required as a composition, and peeling of a pattern generate | occur | produces even if the developing time is more than predetermined time in the image development process during a formation process. However, the interlayer insulating film formed therefrom exhibits good adhesion and is required to have high heat resistance, high solvent resistance, low dielectric constant, high transmittance, and the like. In addition to these, in the case of forming microlenses, a good melt shape (desired curvature radius), high heat resistance, high solvent resistance, and high transmittance are required as the microlens in addition to the above-mentioned various performances, but radiation is satisfied to satisfy such requirements. The resin composition is not known in the prior art.

In addition, there is a concern that the sublimation generated during firing for forming the interlayer insulating film or microlens contaminates the process line or the device, and a radiation-sensitive resin composition in which the generation of the sublimation is reduced is desired.

Conventional Technology Regarding Protective Films

In the process of manufacturing an optical device such as an LCD (liquid crystal display device), a CCD (charge coupled device), a CMOS (complementary metal oxide semiconductor; Complementary Metal 0xide Semiconductor), the display device is a solvent, an acid, an alkali, or the like. Since the surface of the element is locally exposed to high temperatures when applied to the immersion treatment and forming the wiring electrode layer by sputtering, it is resistant to such treatment in order to prevent the display element from being degraded or damaged by such treatment. Providing a protective film having a structure on the surface of the display element is performed.

Such a protective film is required to have high adhesion to a substrate or lower layer on which the protective film is to be formed, and a layer formed on the protective film. In addition, the protective film itself is smooth and tough, has high transparency, high heat resistance and light resistance, does not cause deterioration such as coloration, yellowing and whitening over a long period of time, and is excellent in water resistance, solvent resistance, acid resistance and alkali resistance. Performance is required. Moreover, as a material for forming the protective film which has these various performances, Unexamined-Japanese-Patent No. 5-78453 discloses the thermosetting composition containing the polymer which has glycidyl group.

When such a protective film is used on color filters of LCDs, CCDs and CMOS sensors, it is required to be able to flatten the step by the color filters formed on the base substrate. In addition, in a color liquid crystal display element, for example, a color liquid crystal display element of STN (Super Twisted Nematic) type or TFT (Thin Film Transister) type, it is necessary to maintain the cell gap of the liquid crystal layer uniformly. In order to disperse the bead-shaped spacers on the protective film, the panels are bonded to each other, and the liquid crystal cell is then sealed by thermocompression bonding of the sealing material, but the protective film at the portion where the spacer is present is pitted by the heat and pressure applied at this time. The phenomenon was seen, and the cell gap was wrong. In particular, when manufacturing the STN type color liquid crystal display device, the color filter and the opposing substrate must be bonded strictly with a very high accuracy, and a very high leveling step planarization performance and heat resistance voltage resistance performance are required for the protective film.

In recent years, a method of forming a wiring electrode (ITO: Indium Tin Oxide) by sputtering on a protective film of a color filter and patterning ITO with a strong acid or strong alkali or the like has also been adopted. In this case, the protective film is locally exposed to high temperatures during sputtering or treated with numerous chemicals. Therefore, adhesion to the wiring electrode is also required to withstand such a treatment and to prevent the ITO from peeling off from the protective film during chemical treatment.

In the LCD panel, for the purpose of high brightness, a panel was developed in which a transparent electrode such as ITO and a TFT element were laminated through a highly transparent interlayer insulating film, and the opening area was increased. In addition, although the color filter and the TFT element are conventionally manufactured using separate substrates, a method of forming the color filter on the TFT element has also been developed. In addition, under the technical background, development of a protective film having high heat resistance and excellent performance (flattening capability) for flattening a step of a color filter formed on a base substrate is desired.

In addition, with the recent increase in the size of the panel substrate, a sublimation is generated in the firing step of forming a protective film from the thermosetting composition and is deposited inside the firing furnace, contaminating the firing furnace, making it difficult to control the firing conditions, It is a problem to adhere to the panel substrate and to contaminate it to induce display defects.

Although it is suitable to use the curable resin composition which has the advantage that the protective film excellent in surface hardness can be formed easily for formation of the protective film for color filters, it does not only satisfy | fill the general required performance as a protective film, such as transparency, The material which can form the protective film which can respond to a new high demand, and is excellent in the storage stability as a composition is still unknown.

The present invention has been made on the basis of the above circumstances, and an object thereof is firstly to have a high radiation sensitivity, a sufficiently high resolution, excellent adhesion to a substrate or a base or an upper layer, and generation of a sublimation during firing of a film forming process. It is to provide this suppressed curable resin composition.

The curable resin composition provides a spacer excellent in pattern shape, compressive strength and rubbing resistance when used for formation of the spacer;

When used to form an interlayer insulating film, the so-called "development margin" is large, and high heat resistance and high permeability, which are indices for forming a good pattern shape even if the development continues beyond the optimum developing time in the developing step. A low dielectric constant interlayer insulating film can be formed;

When used for the formation of microlenses, it is possible to form microlenses having a high development margin and having a high light transmittance and a good melt shape.

Secondly, the object of the present invention is excellent adhesion to the substrate or the substrate or the upper layer, and suppresses the generation of sublimation during firing of the film forming process, and also satisfies high transparency, high heat resistance and high surface hardness while heating It is providing the curable resin composition which can form the protective film which is excellent in load resistance below, and is excellent in the ability to planarize the level | step difference of the color filter formed on the base substrate.

It is a third object of the present invention to provide a method for forming a cured film from any of the above curable resin compositions.

An object of the present invention is, fourthly, to provide a cured film formed by the above method.

According to the present invention, the above object of the present invention firstly,

(A) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of polystyrene conversion measured by gel permeation chromatography, polymerized by living radical polymerization in the presence of the compound represented by the following formula (1). Is 1.7 or less, and it is achieved by the curable resin composition containing the polymer which has a carboxyl group.

Wherein two Z's each independently represent a hydrogen atom, a carboxyl group, a group -R, a group -OR, a group -NR ₂ , a group -COOR, a group -C (= 0) NR ₂ , and a group -P (= 0) R ₂ , a group -P (= O) (OR) ₂ or a group -NRNR-C (= O) R, R is independently a halogen atom, cyano group, hydroxyl group, alkyl group having 1 to 20 carbon atoms, 2 to 20 carbon atoms Is an alkenyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a monovalent heterocyclic group having 3 to 20 atoms in total having a carbon atom and a hetero atom, and R is an alkyl group, an alkenyl group, or an aryl group , In the case of an aralkyl group or a heterocyclic group, one or more of hydrogen atoms of R may be substituted with a halogen atom, cyano group, hydroxyl group or carboxyl group.)

The composition is preferably used for formation of spacers, formation of an interlayer insulating film or microlens, or formation of a protective film.

The above object of the present invention is secondly (A ′) polymerized by living radical polymerization in the presence of the compound represented by the formula (1), and the weight average molecular weight (Mw) and the number average of polystyrene conversion measured by gel permeation chromatography. Achieved by a curable resin composition containing a polymer having an oxiranyl group or an oxetanyl group and a (E) cationic polymerizable compound having a ratio (Mw / Mn) of a molecular weight (Mn) of 1.7 or less and used for forming a protective film. do.

The above object of the present invention is thirdly achieved by a method of forming a spacer, an interlayer insulating film or a microlens or a protective film using any of the above curable compositions.

In addition, the above object of the present invention is fourthly achieved by a spacer, an interlayer insulating film or a microlens or a protective film formed by the method.

Best Mode for Carrying Out the Invention

<< curable resin composition >>

Curable resin composition of this invention contains the said (A) polymer or (A ') polymer.

(A) The polymer is polymerized by living radical polymerization in the presence of the compound represented by the formula (1), and the ratio (Mw) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography. / Mn) is 1.7 or less and a polymer having a carboxyl group, preferably a polymer having an oxiranyl group or an oxetanyl group in addition to the carboxyl group.

On the other hand, the polymer (A ') is polymerized by living radical polymerization in the presence of the compound represented by the formula (1), and the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography. The ratio (Mw / Mn) is 1.7 or less, and is a polymer having an oxiranyl group or an oxetanyl group, preferably two or more oxiranyl groups or oxetanyl groups in the molecule, an acetal structure, a ketal structure, and t- A polymer having one or more structures selected from the group consisting of butoxycarbonyl structures (hereinafter referred to as "polymer (A'1)") or a molecule having two or more oxiranyl groups or oxetanyl groups, and a carboxyl group , A copolymer having no carboxylic acid anhydride group, acetal structure, ketal structure and t-butoxycarbonyl structure (hereinafter referred to as "polymer (A'2)").

The acetal structure or the ketal structure refers to a structure in which an acetal forming group or a ketal forming group as described below is bonded to a carbon atom. The polymer having an acetal structure or a ketal structure refers to a polymer in which an acetal-forming group or a ketal-forming group such as described below is bonded directly to a carbon atom in the polymer or through a bonding water such as a carbonyl group. .

As a functional group (henceforth "acetal formation group") which can form an acetal structure, it is a 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-i-propoxyethoxy group, 1-n-butoxyethoxy group, 1-i-butoxyethoxy group, 1-sec-butoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclopentyloxyethoxy group, 1-cyclohexyloxyethoxy group, 1-norbornyloxyethoxy group, 1-bornyloxyethoxy group, 1-phenoxyethoxy group, 1- (1- Naphthyloxy) ethoxy group, 1-benzyloxyethoxy group, 1-phenethyloxyethoxy group, (cyclohexyl) (methoxy) methoxy group, (cyclohexyl) (ethoxy) methoxy group, (cyclohexyl) (n-propoxy) methoxy group, (cyclohexyl) (i-propoxy) methoxy group, (cyclohexyl) (cyclohexyloxy) methoxy group, (cyclohexyl) (phenoxy) methoxy group, (cyclohexyl) (Benzyloxy) methoxy group, (phenyl) (methoxy) methoxy group, (phenyl) (ethoxy) methoxy group, (phenyl) (n -Propoxy) methoxy group, (phenyl) (i-propoxy) methoxy group, (phenyl) (cyclohexyloxy) methoxy group, (phenyl) (phenoxy) methoxy group, (phenyl) (benzyloxy) methoxy group , (Benzyl) (methoxy) methoxy group, (benzyl) (ethoxy) methoxy group, (benzyl) (n-propoxy) methoxy group, (benzyl) (i-propoxy) methoxy group, (benzyl) (cyclo Hexyloxy) methoxy group, (benzyl) (phenoxy) methoxy group, (benzyl) (benzyloxy) methoxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyloxy group, etc. are mentioned. Among these acetal-forming groups, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydropyranyloxy group, 2-tetrahydropyranyloxy group, etc. desirable.

Moreover, as a functional group (henceforth a "ketal formation group") which can form a ketal structure, it is a 1-methyl-1- methoxyethoxy group, 1-methyl-1- ethoxyethoxy group, 1-methyl-1-n-propoxyethoxy group, 1-methyl-1-i-propoxyethoxy group, 1-methyl-1-n-butoxyethoxy group, 1-methyl-1-i- Butoxyethoxy group, 1-methyl-1-sec-butoxyethoxy group, 1-methyl-1-t-butoxyethoxy group, l-methyl-1-cyclopentyloxyethoxy group, 1-methyl -1-cyclohexyloxyethoxy group, 1-methyl-1-norbornyloxyethoxy group, 1-methyl-1-bornyloxyethoxy group, 1-methyl-1-phenoxyethoxy group, 1 -Methyl-1- (1-naphthyloxy) ethoxy group, 1-methyl-1-benzyloxyethoxy group, 1-methyl-1-phenethyloxyethoxy group, 1-cyclohexyl-1-methoxy Oxy group, 1-cyclohexyl-1-ethoxyethoxy group, 1-cyclohexyl-1-n-propoxyethoxy group, 1-cyclohexyl-1-i-propoxyethoxy group, 1-cyclohexyl -1-cyclohexyloxyethoxy group, 1-cyclo Sil-1-phenoxyethoxy group, 1-cyclohexyl-1-benzyloxyethoxy group, 1-phenyl-1-methoxyethoxy group, 1-phenyl-1-ethoxyethoxy group, 1-phenyl -1-n-propoxyethoxy group, 1-phenyl-1-i-propoxyethoxy group, 1-phenyl-1-cyclohexyloxyethoxy group, 1-phenyl-1-phenoxyethoxy group, 1-phenyl-1-benzyloxyethoxy group, 1-benzyl-1-methoxyethoxy group, 1-benzyl-1-ethoxyethoxy group, 1-benzyl-1-n-propoxyethoxy group, 1-benzyl-1-i-propoxyethoxy group, 1-benzyl-1-cyclohexyloxyethoxy group, 1-benzyl-1-phenoxyethoxy group, 1-benzyl-1-benzyloxyethoxy group , 1-methoxycyclopentyloxy group, 1-methoxycyclohexyloxy group, 2- (2-methyltetrahydrofuranyl) oxy group, 2- (2-methyltetrahydropyranyl) oxy group, and the like. have. Among these ketal forming functional groups, 1-methyl-1-methoxyethoxy group or 1-methyl-1-cyclohexyloxyethoxy group is preferable.

The polymer (A) is at least one selected from (a1) unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter collectively referred to as "compound (a1)"), (a2) oxiranyl group or oxetanyl Unsaturated compounds containing groups (hereinafter referred to as "compound (a2)") and unsaturated compounds other than (a3) (a1) and (a2) also have acetal structure, ketal structure or t-butoxycarbonyl structure in the molecule. It is preferable that it is a polymer obtained by living radical polymerization of the polymeric mixture containing an unsaturated compound (henceforth "a compound (a3)") in presence of the compound represented by the said General formula (1).

For example, the polymer (A) is prepared by living radical polymerization of a polymerizable mixture containing a compound (a1), a compound (a2) and a compound (a3) in a suitable solvent in the presence of a polymerization initiator and the compound represented by the formula (1). It is desirable to. The carboxyl group which the polymer (A) thus obtained has is derived from compound (a1), and the oxiranyl group or oxetanyl group is derived from compound (a2).

The polymer (A'1) is preferably an unsaturated compound having at least one structure selected from the group consisting of acetal structure, ketal structure and t-butoxycarbonyl structure in compound (a2), compound (a3) and molecule ( Hereinafter, it is a polymer obtained by living radical polymerization of the polymeric mixture containing "compound (a4)" in presence of a polymerization initiator and the compound represented by the said Formula (1) in a suitable solvent. Further, the polymer (A'2) is preferably a polymer obtained by living radical polymerization of a polymerizable mixture containing a compound (a2) and a compound (a3) in a suitable solvent in the presence of a polymerization initiator and the compound represented by the above formula (1). to be.

It is preferable that all the said compounds (a1)-(a4) have radical polymerizability.

Hereinafter, living radical polymerization for producing (A) polymer or (A ') polymer is demonstrated.

Various proposals have been made for a radical polymerization initiator system for living radical polymerization of a polymerizable unsaturated compound or a mixture thereof, for example in M. K. Georges et al., Macromolecules, 1993, Vol. 26, p. 2987, the so-called TEMPO system; Matyjaszewski et al., Macromolecules, 1997, Vol. 30, p.7348, disclose a system consisting of a combination of copper bromide and bromine containing ester compounds; Hamasaki, S. et al., Macromolecules, 2002, Vol. 35, p. 2934, include systems consisting of a combination of carbon tetrachloride and ruthenium (II) complexes; Japanese Patent 3639859 (Japanese Patent Publication 2000-515181), Japanese Patent Publication 2002-500251, Japanese Patent Publication 2004-518773, Japanese Patent Publication 2002-508409, Japanese Patent Publication 2002-512653, Japanese Patent Publication 2003 -527458, Japanese Patent No. 3634843 (Japanese Patent Publication No. 2003-536105) and Japanese Patent Publication No. 2005-503452 have systems each consisting of a combination of a thiocarbonylthio compound and a radical initiator having a chain transfer constant greater than 0.1, respectively. Is disclosed.

However, the present inventors found that curable resin compositions containing a polymer having a specific structure obtained by living radical polymerization using a specific thiocarbonylthio compound satisfy various required characteristics as a cured film, and also generate sublimation during firing of the film forming process. This is found to be suppressed, and the present invention has been reached.

In the living radical polymerization for synthesizing the polymer used in the present invention, the compound represented by Chemical Formula 1 is used.

As a halogen atom of Z in the said General formula (1), For example, a chlorine atom, a bromine atom, a fluorine atom, etc .;

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, 1,1-dimethylpropyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1-dimethyl-3,3-dimethylbutyl group, n-nonyl group, n-decyl group , n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n-eicosyl group, etc .; Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl group, allyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, and 2-butenyl group;

Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 9-anthracenyl group and the like;

Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group and phenethyl group;

Examples of the monovalent heterocyclic group having 3 to 20 carbon atoms in total with a hetero atom include, for example, an oxiranyl group, an aziridinyl group, a 2-furanyl group, a 3-furanyl group, a 2-tetrahydrofuranyl group, and 3 Tetrahydrofuranyl group, pyrrole-1-yl group, pyrrole-2-yl group, pyrrole-3-yl group, 1-pyrrolidinyl group, 2-pyrrolidinyl group, 3-pyrrolidinyl group, pyrazole-1 -Yl group, pyrazol-3-yl group, 2-tetrahydropyranyl group, 3-tetrahydropyranyl group, 4-tetrahydropyranyl group, 2-tianyl group, 3-tianyl group, 4-tianyl group, 2 -Pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 2-piperidinyl group, 3-piperidinyl group, 4-piperidinyl group, 2-morpholinyl group, 3-morpholinyl group, 2-imi Dazolyl group, 4-imidazolyl group, indol-1-yl group, etc. are mentioned, respectively.

As a preferable specific example of Z in the said General formula 1, a hydrogen atom, a cyano group, a chlorine atom, a carboxyl group, a dodecyl group, an octadecyl group, an ethoxy group, butoxycarbonyl group, a phenyl group, a phenoxy group, a dimethylamino group, di Ethylamino group, dimethylaminocarbonyl group, diethylaminocarbonyl group, 2-imidazolyl group, pyrrole-1-yl group, pyrazol-1-yl group, 3-methyl-pyrazol-1-yl group, 4-methyl-pyrazole- 1-Diol, Indol-1-yl, Group -P (= O) (OC ₂ H ₅ ) ₂ , Group -P (= O) (C ₆ H ₅ ) ₂ , Group -P (= O) (OC ₆ H ₅ ) ₂ , group -N (C ₂ H ₅ ) N (CH ₃ ) C (= O) CH ₂ F, group -N (C ₆ H ₅ ) ₂ , group -N (C ₆ H ₅ ) CH ₃ Etc. can be mentioned.

Preferable specific examples of the compound represented by the formula (1) include, for example, tetraethylthiuram disulfide, bis (pyrazol-1-ylthiocarbonyl) disulfide, bis (3-methyl-pyrazol-1-ylthio Carbonyl) disulfide, bis (4-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bispyrrole-1-ylthiocarbonyl disulfide, bisthiobenzoyl disulfide and the like.

These compounds can be used individually or in mixture of 2 or more types.

It does not specifically limit as a radical polymerization initiator used for a living radical polymerization, What is generally known as a radical polymerization initiator can be used, For example, 2,2'- azobisisobutyronitrile and 2,2'- azobis Azo compounds such as (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, 1,1'-bis (t-butylperoxy) cyclohexane and t-butylperoxy pivalate; Hydrogen peroxide; And redox initiators composed of these peroxides and reducing agents.

These radical initiators can be used individually or in mixture of 2 or more types.

The solvent used for the living radical polymerization is not particularly limited as long as the active radical is inactivated, but for example, propylene glycol monoalkyl ether compounds such as propylene glycol monomethyl ether and propylene glycol monoethyl ether;

Ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether (Poly) alkylene glycol alkyl ether acetate compounds such as acetate;

(Poly) alkylene glycol dialkyl such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether Ether compounds;

Other ether compounds such as tetrahydrofuran;

Ketone compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

Ketoalcohol compounds such as diacetone alcohol (ie, 4-hydroxy-4-methylpentan-2-one) and 4-hydroxy-4-methylhexan-2-one;

Lactic acid alkyl ester compounds such as methyl lactate and ethyl lactate;

Ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 Ethyl ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n acetate -Butyl, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-pyruvate Other ester compounds such as propyl, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate;

Aromatic hydrocarbon compounds such as toluene and xylene;

And amide compounds such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, from the viewpoints of solubility of each component when forming the curable resin composition, film formation properties, and the like, Dipropylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 3-methoxypropionate, 3-e Methyl oxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, n-butyl propionate, butyric acid Ethyl, butyric acid i-propyl, n-butyl butyrate, ethyl pyruvate and the like are preferred.

The said solvent can be used individually or in mixture of 2 or more types.

It is preferable that the usage-amount of a solvent is 50-1,000 weight part with respect to 100 weight part of total unsaturated compounds, More preferably, it is 100-500 weight part.

In the living radical polymerization, the amount of the compound represented by Formula 1 is preferably 0.1 to 50 parts by weight, more preferably 0.2 to 16 parts by weight, and more preferably 0.4 to 8 parts by weight based on 100 parts by weight of the total unsaturated compound. desirable. When this value is less than 0.1 weight part, the control effect of molecular weight and molecular weight distribution may be inadequate, and when this value exceeds 50 weight part, there exists a possibility that a low molecular weight component may produce | generate preferentially. It is preferable that the usage-amount of a radical polymerization initiator is 0.1-50 weight part with respect to 100 weight part of total unsaturated compounds, More preferably, it is 0.1-20 weight part. It is preferable that polymerization temperature is 0-150 degreeC, More preferably, it is 50-120 degreeC, It is preferable that polymerization time is 10 minutes-20 hours, More preferably, it is 30 minutes-6 hours.

The compound (a1) which is preferably used for synthesizing the polymer (A) is one or more selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides having radical polymerizability.

As the compound (a1), for example, monocarboxylic acid, dicarboxylic acid, anhydride of dicarboxylic acid, mono [(meth) acryloyloxyalkyl] ester of polyhydric carboxylic acid, and a carboxyl group at each of both terminals, for example. And mono (meth) acrylate of a polymer having a hydroxyl group, a polycyclic compound having a carboxyl group, and anhydrides thereof. In addition, in this specification, "(meth) acrylate" is the concept which integrated the acrylate and methacrylate. Other similar terms such as "(meth) acryloyloxy group" should be understood in the same way.

As a specific example of these, As a monocarboxylic acid, For example, acrylic acid, methacrylic acid, crotonic acid, etc .;

As the dicarboxylic acid, for example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;

As anhydride of dicarboxylic acid, For example, acid anhydride of the said compound illustrated as said dicarboxylic acid;

As mono [(meth) acryloyloxyalkyl] ester of polyhydric carboxylic acid, For example, succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl ] Etc;

As mono (meth) acrylate of the polymer which has a carboxyl group and a hydroxyl group in each of both terminal, For example, (omega) -carboxypolycaprolactone mono (meth) acrylate etc .;

As the polycyclic compound having a carboxyl group and anhydrides thereof, for example, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5 -Carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2 .1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, and the like. Each can be mentioned.

Among these, anhydrides of monocarboxylic acid and dicarboxylic acid are preferably used, and acrylic acid, methacrylic acid and maleic anhydride are particularly preferably used in view of copolymerization reactivity, solubility in an aqueous alkali solution and easy availability. These are used alone or in combination.

In the living radical polymerization, the carboxyl group or acid anhydride group of the compound (a1) may be protected by a suitable protecting group and polymerized, followed by deprotection.

Compound (a2) which is preferably used for synthesizing the (A) polymer or the (A ') polymer is an unsaturated compound having radical polymerizability and containing an oxiranyl group or an oxetanyl group.

As a compound (a2) which has an oxiranyl group, for example, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycidyl (alpha)-n-propyl acrylate, the glycine (alpha)-n-butyl acrylate Cedyl, 3,4-Oxiranylbutyl acrylate, 3,4-Oxiranylbutyl methacrylate, 3,4-Oxiranylbutyl α-ethyl acrylate, 6,7-Oxiranylheptyl acrylate, 6,7 methacrylate -Oxyranylheptyl, α-ethylacrylic acid 6,7-oxyranylheptyl, acrylic acid β-methylglycidyl, methacrylic acid β-methylglycidyl, acrylic acid β-ethylglycidyl, methacrylic acid β-ethylglycol Oxiranyl, such as cydyl, (beta) -n-propylglycidyl acrylate, (beta) -n-propylglycidyl methacrylate, 3, 4- oxiranyl cyclohexyl acrylate, 3, 4- oxiranyl cyclohexyl methacrylate Carboxylic acid ester compound which has a group;

and ether compounds having an oxiranyl group such as o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether.

Moreover, as a compound (a2) which has an oxetanyl group, 3-ethyl-3- oxetanyl acrylate, 3-ethyl-3- oxetanyl methacrylate, etc. are mentioned, for example.

Of these compounds (a2), methacrylic acid glycidyl, methacrylic acid 6,7-oxiranylheptyl, methacrylic acid 3,4-oxyranylcyclohexyl, methacrylic acid β-methylglycidyl, o-vinyl Benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3-ethyl-3-oxetanyl methacrylic acid, etc. are preferable at the point of copolymerization reactivity and the intensity | strength of the cured film obtained. Do.

The said compound (a2) can be used individually or in mixture of 2 or more types.

Compound (a3), which is preferably used for synthesizing the (A) polymer or the (A ') polymer, is an unsaturated compound having radical polymerizability other than (a1) and (a2) as an acetal structure, a ketal structure, or t- in a molecule. It is an unsaturated compound which does not have a butoxycarbonyl structure.

As the compound (a3), for example, methacrylic acid alkyl ester, acrylic acid alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid ester having a hydroxyl group, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, An unsaturated dicarboxylic acid diester, a bicyclo unsaturated compound, a maleimide compound, an unsaturated aromatic compound, conjugated diene, etc. are mentioned.

As specific examples of these, as methacrylic acid alkyl esters, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate and 2-ethylhexyl methacrylate Acrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate and the like;

As alkyl acrylate, For example, methyl acrylate, isopropyl acrylate, etc .;

As methacrylic acid cyclic alkylester, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8- ^yloxyethyl methacrylate, isoboroyl methacrylate, and the like;

As methacrylic acid ester which has a hydroxyl group, For example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol mono Methacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethylglycoside, 4-hydroxyphenyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate and the like;

As acrylic acid cyclic alkylester, For example, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] Decan-8-yloxyethyl acrylate, isoboroyl acrylate and the like;

As methacrylic acid aryl ester, For example, phenyl methacrylate, benzyl methacrylate;

As acrylic acid aryl ester, For example, phenyl acrylate, benzyl acrylate;

As unsaturated dicarboxylic acid diester, For example, diethyl maleate, diethyl fumarate, diethyl itaconic acid;

As the bicyclo unsaturated compound, for example, bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept 2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyl ox Cycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2.2 .1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene , 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5- Hydroxy-5-ethylbicycle [2.2.1] hept-2-ene, and 5-hydroxy-5-methyl-bicyclo [2.2.1] hept-2-ene;

As the maleimide compound, for example, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide Butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide and the like;

As an unsaturated aromatic compound, For example, styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy styrene etc .;

As the conjugated diene, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like;

As other unsaturated compounds, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, methacrylic acid tetrahydrofurfuryl, etc. are mentioned, for example.

Of these, methacrylic acid alkyl esters, methacrylic acid cyclic alkyl esters, methacrylic acid esters having a hydroxyl group, bicyclounsaturated compounds, unsaturated aromatic compounds, conjugated dienes and the like are preferably used, among which styrene and t-butyl methacrylate are used. , Tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, p-methoxystyrene, 2-methylcyclohexylacrylate, 1,3-butadiene, polyethyleneglycol monomethacrylate, polypropylene Glycol monomethacrylate, bicyclo [2.2.1] hept-2-ene or tetrahydrofurfuryl methacrylate are particularly preferred in view of copolymerization reactivity and solubility in aqueous alkali solution. These are used alone or in combination.

Compound (a4) which is preferably used for synthesizing the polymer (A ') is an unsaturated compound having at least one structure selected from the group consisting of an acetal structure, a ketal structure and a t-butoxycarbonyl structure in the molecule.

As the compound (a4), a norbornene-based compound having one or more structures selected from the group consisting of an acetal structure, a ketal structure and a t-butoxycarbonyl structure (hereinafter referred to as a "specific norbornene-based compound") and an acetal structure And (meth) acrylic acid ester compound (henceforth "a specific (meth) acrylic acid ester compound") which has 1 or more types of structure chosen from the group which consists of a ketal structure, t-butyl (meth) acrylic acid, etc. are mentioned.

Specific examples of the specific norbornene-based compound include, for example, 2,3-di (1-methoxyethoxycarbonyl) -5-norbornene and 2,3-di (1-t-butoxyethoxycar Bonyl) -5-norbornene, 2,3-di (1-benzyloxyethoxycarbonyl) -5-norbornene, 2,3-di (1-methyl-1-methoxyethoxycarbonyl) -5-norbornene, 2,3-di (1-methyl-1-i-butoxyethoxycarbonyl) -5-norbornene, 2,3-di ((cyclohexyl) (ethoxy) meth Oxycarbonyl) -5-norbornene, 2,3-di ((benzyl) (ethoxy) methoxycarbonyl) -5-norbornene, 2,3-di (tetrahydrofuran-2-yloxyca Carbonyl) -5-norbornene, 2,3-di (tetrahydropyran-2-yloxycarbonyl) -5-norbornene, 2,3-di (t-butoxycarbonyl) -5- Norbornene etc. are mentioned.

As a specific example of the said specific (meth) acrylic acid ester compound, (meth) acrylic acid 1-ethoxyethyl, (meth) acrylic acid 1-n-propoxyethyl, (meth) acrylic acid 1-n-butoxyethyl, ( 1-i-butoxyethyl methacrylate, 1- (cyclopentyloxy) ethyl (meth) acrylate, 1- (cyclohexyloxy) ethyl (meth) acrylate, 1- (1,1-dimethyl meth) acrylate Ethoxy) ethyl, (meth) acrylic acid tetrahydro-2H-pyran-2-yl, etc. are mentioned.

Among these compounds (a4), specific (meth) acrylic acid ester compounds or t-butyl (meth) acrylate are preferable, and in particular, methacrylic acid 1-ethoxyethyl, methacrylic acid 1-i-butoxyethyl and methacrylic acid 1- (cyclopentyloxy) ethyl, methacrylic acid 1- (cyclohexyloxy) ethyl, methacrylic acid 1- (1,1-dimethylethoxy) ethyl, methacrylic acid tetrahydro-2H-pyran-2- Preference is given to mono or methacrylic acid t-butyl. These preferable compounds (a4) are effective in raising the heat resistance and surface hardness of the cured film obtained while producing the curable resin composition which is high in copolymerization reactivity, and is excellent in storage stability and planarization ability.

The said unsaturated compound (a4) can be used individually or in mixture of 2 or more types.

As described above, the polymer (A) is preferably a polymer obtained by living radical polymerization of a polymerizable mixture containing a compound (a1), a compound (a2) and a compound (a3) in the presence of the compound represented by the above formula (1). It is preferable.

On the other hand, polymer (A'1), which is one of preferred embodiments of the polymer (A '), is a polymerizable mixture containing a compound (a2), a compound (a3) and a compound (a4) in the presence of the compound represented by the formula (1) It is preferable that it is a polymer obtained by living radical polymerization under the following. In addition, polymer (A'2), which is another preferred embodiment of the polymer (A '), preferably contains a polymerizable mixture containing the compound (a2) and the compound (a3) in the presence of the compound represented by the formula (1). It is a polymer obtained by radical polymerization.

In the polymer (A), the content of the structural unit derived from the compound (a1) is preferably 5 to 50% by weight based on the sum of the structural units derived from the compound (a1), (a2) and (a3), More preferably, it is 10-40 weight%, and it is preferable that it is 10-30 weight%. In this case, when the content rate of the said structural unit is less than 5 weight%, there exists a tendency for the intensity | strength, heat resistance, and chemical-resistance of the cured film obtained to fall, and when it exceeds 50 weight%, the storage stability of curable resin composition may fall. have.

The polymer (A) used in the present invention is preferably 10 to 70% by weight based on the sum of the structural units derived from the compounds (a1), (a2) and (a3). Especially preferably, it contains 20 to 60 weight%. When this structural unit is less than 10 weight%, there exists a tendency for the heat resistance and surface hardness of the cured film obtained to fall, and when the quantity of this structural unit exceeds 70 weight%, there exists a tendency for the storage stability of curable resin composition to fall. have.

The polymer (A) used in the present invention is preferably 5 to 70% by weight based on the sum of the structural units derived from the compounds (a1), (a2) and (a3). More preferably, it contains 10 to 60 weight%, More preferably, it is 20 to 50 weight%. When this structural unit is less than 5 weight%, there exists a tendency for the storage stability of curable resin composition to fall, and when it exceeds 70 weight%, it becomes difficult to melt | dissolve in aqueous alkali solution in the image development process in formation of a cured film. have.

The content of the repeating unit derived from the compound (a2) in the polymer (A'1) is preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight based on the total repeating units. When the content rate of the repeating unit derived from a compound (a2) is less than 10 weight%, there exists a tendency for the heat resistance and surface hardness of a protective film to fall, and when it exceeds 70 weight%, there exists a tendency for the storage stability of a composition to fall.

The content of the repeating unit derived from compound (a4) in the polymer (A'1) is preferably 5 to 60% by weight, particularly preferably 10 to 50% by weight. By making the content rate of the repeating unit derived from a compound (a4) into this range, the favorable heat resistance and surface hardness of a protective film can be implement | achieved.

Although the content rate of the repeating unit derived from the compound (a3) in a polymer (A'1) is the quantity which subtracted the total content rate of the repeating unit derived from a compound (a2) and a compound (a4) from 100 weight%, Preferably it is It is 10-80 weight% with respect to all the repeating units, More preferably, it is 20-60 weight%.

The content of the repeating unit derived from the compound (a2) in the polymer (A'2) is preferably 1 to 90% by weight, particularly preferably 40 to 90% by weight based on the total repeating units. When the content rate of the repeating unit derived from a compound (a2) is less than 1 weight%, there exists a tendency for the heat resistance and surface hardness of a cured film to fall, and when it exceeds 90 weight%, there exists a tendency for the storage stability of a composition to fall.

The content rate of the repeating unit derived from the compound (a3) in a (A'2) polymer is the quantity which subtracted the content rate of the repeating unit derived from a compound (a2) from 100 weight%.

As mentioned above, although the (A) polymer or (A ') polymer used by this invention is obtained by living radical polymerization of an unsaturated compound, the compound represented by the said Formula (1) at the time of a living radical polymerization uses the molecular weight controlling agent. For this reason, the polymer (A) and the polymer (A ') have a group represented by the following formula (1a) derived from the compound represented by the formula (1) in the polymer. The group represented by the formula (1a) is preferably located at the end of the (A) polymer or (A ') polymer.

(Wherein Z is the same as that in Formula 1).

The (A) polymer or (A ') polymer used by this invention is a polystyrene conversion weight average molecular weight (henceforth "Mw") measured by gel permeation chromatography, and polystyrene conversion number average molecular weight (henceforth "Mn"). Ratio (Mw / Mn) is 1.7 or less, and preferably 1.5 or less. When Mw / Mn exceeds 1.7, the heat resistance of the obtained cured film may be insufficient. Mw is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ³ to 5 × 10 ⁴ . When Mw is less than 2 * 10 <^3> , the applicability | paintability of a composition may become inadequate or the heat resistance of the cured film obtained may be inadequate. On the other hand, when Mw exceeds 1 * 10 < ⁵ >, the sensitivity or the planarization performance of the cured film obtained may become inadequate. Mn is preferably 1.2 × 10 ³ to 1 × 10 ⁵ , and more preferably 2.9 × 10 ³ to 5 × 10 ⁴ . In addition, the ratio Mw / Mn should be evaluated with a precision of two significant digits (one decimal point or less).

In addition, the residual monomer amount measured by gel permeation chromatography of the polymer (A) or the polymer (A ') used in the present invention is preferably less than 5.0%, more preferably less than 3.0%, particularly preferably 2.0% Is less than. By using the copolymer of such residual monomer content, curable resin composition in which the sublimation at the time of baking is reduced can be obtained.

Curable resin composition of this invention contains the above-mentioned (A) polymer or (A ') polymer. Curable resin composition of this invention can also replace a part of (A) polymer or (A ') polymer with another polymer in the range which does not impair the effect of this invention. In this case, other polymers specially synthesized corresponding to the preparation of the composition may be mixed or used, or in the synthesis of the polymer (A) or the polymer (A ′), a molecular weight control agent different from the compound represented by the formula (1), for example For example, it can also be followed by the method of synthesizing and using another polymer with (A) polymer or (A ') polymer by using together 1 or more types, such as (alpha) -methyl styrene dimer and t-dodecyl mercaptan. In the case of the latter method, the amount of the other molecular weight controlling agent is preferably 200 parts by weight or less, more preferably 40 parts by weight or less based on 100 parts by weight of the compound represented by the formula (1). When the usage-amount of another molecular weight control agent exceeds 200 weight part, the effect of this invention may be impaired.

The curable resin composition containing the polymer (A) is preferably a composition containing (B) a polymerizable unsaturated compound and (C) a radiation sensitive polymerization initiator in addition to the polymer (A) (hereinafter referred to as "first composition"). ), (A) a composition containing (D) 1,2-quinonediazide compound in addition to the polymer (hereinafter sometimes referred to as "second composition") or (A) polymer other than (E) cationic polymerizable It is a composition containing a compound (henceforth a "third composition"). The third composition preferably further contains a (F) curing agent or (G) acid generator.

On the other hand, the curable resin composition containing the (A ') polymer is preferably a composition containing the (E) cationically polymerizable compound in addition to the (A') polymer (hereinafter sometimes referred to as "fourth composition"), Or the two-component curable resin composition (hereinafter, referred to as "the fifth composition") comprising the first liquid containing the (A ') polymer and the (E) cationically polymerizable compound and the second liquid containing the (F) curing agent. Yes). As (A ') polymer here, in a 4th composition, Preferably it is the said (A'1) polymer or (A'2) polymer, and in a 5th composition, it is the said (A'2) polymer. The fourth composition preferably further contains a (F) curing agent or (G) acid generator.

Hereinafter, the first to fifth compositions will be described in order.

<1st composition>

The first composition is preferably a radiation sensitive resin composition containing (A) a polymer, (B) a polymerizable unsaturated compound and (C) a radiation sensitive polymerization initiator.

Preferred specific examples of the polymer (A) used in the first composition include, for example, styrene / methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / glycidyl methacrylate air Copolymer, styrene / methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / glycidyl methacrylate / 1,3-butadiene copolymer, styrene / methacrylic acid / acrylic acid / Benzyl methacrylate / n-butyl methacrylate 3-ethyl-3-oxetanyl copolymer of methacrylate, styrene / methacrylic acid / benzyl methacrylate / methacrylate tetrahydrofurfuryl / methyl methacrylate Glycidyl copolymer etc. are mentioned.

As (B) polymerizable unsaturated compound used preferably for a 1st composition, (meth) acrylate more than bifunctional is preferable.

As a bifunctional (meth) acrylate, for example, ethylene glycol acrylate, ethylene glycol methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonane Diol diacrylate, 1,9-nonanediol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, bisphenoxy Ethanol fluorene diacrylate, bisphenoxyethanol fluorene dimethacrylate, and the like.

As a commercial item of such a bifunctional (meth) acrylate, For example, Alonics M-210, M-240, M-6200 (above, Toagosei Co., Ltd.), KAYARAD HDDA, KAYARAD HX-220, East R-604, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, MU-2100, MU-4001 (above, Nippon Kayaku Co., Ltd.), biscoat 260, copper 312, copper 335HP (above, manufactured by Osaka Yuki Chemical Co., Ltd.), etc. are mentioned.

As a trifunctional or more than (meth) acrylate, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acryloyloxy In addition to ethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, and the like, a compound having a linear alkylene group and an alicyclic structure and also having two or more isocyanate groups, and having one or more hydroxyl groups in the molecule, When obtained by reacting a compound having five (meth) acryloyloxy groups There may be mentioned carbon acrylate-based compound and the like.

As a commercial item of the trifunctional or more than (meth) acrylate, For example, Alonics M-309, copper-400, copper-402, copper-405, copper-450, copper-1310, copper-1600, copper-1960, copper -7100, East-8030, East-8060, East-8100, East-8530, East-8560, East-9050, Alonics TO-1450 (above, manufactured by Toa Kosei Co., Ltd.), KAYARAD TMPTA, East DPHA, East DPCA-20, copper DPCA-30, copper DPCA-60, copper DPCA-120, copper MAX-3510 (above, manufactured by Nippon Kayaku Co., Ltd.), biscot 295, copper 300, copper 360, copper GPT, copper 3PA 400 (above, Osaka Yuki Kagaku Kogyo Co., Ltd.) B, as a urethane acrylate compound, New Frontier R-1150 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD DPHA-40H (Nipbon Kayaku ( Note) manufacture) etc. are mentioned.

In this invention, (B) polymerizable unsaturated compound can be used individually or in mixture of 2 or more types.

The usage-amount of the (B) polymerizable unsaturated compound in a 1st composition becomes like this. Preferably it is 10-150 weight part with respect to 100 weight part of (A) polymers, More preferably, it is 20-120 weight part. When the usage-amount of (B) polymerizable unsaturated compound is less than 10 weight part, it will become difficult to form a coating film with a uniform film thickness, and when it exceeds 150 weight part, there exists a tendency for adhesiveness with a board | substrate to fall.

The radiation sensitive polymerization initiator (C) which is preferably used in the first composition is a component that generates active species capable of initiating polymerization of the (B) polymerizable unsaturated compound in response to radiation.

As such a (C) radiation sensitive polymerization initiator, a radiation sensitive radical polymerization initiator can be used preferably, for example.

As said radiation sensitive radical polymerization initiator, For example, alpha-diketones, such as diacetyl;

Acyloins such as benzoin; Acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; Thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzo Benzophenones such as phenone; Acetophenone, p-dimethylaminoacetophenone, 4- (α, α'-dimethoxyacetoxy) benzophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2- Methyl-2-morpholino-1- (4-methylthiophenyl) -1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, etc. Acetophenones; Quinones such as anthraquinone and 1,4-naphthoquinone; Halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone and tris (trichloromethyl) -s-triazine; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphineoxide, bis (2,4,6-trimethylbenzoyl) phenylforce Acylphosphine oxides such as pinoxide; Organic peroxides, such as di-t-butyl peroxide, etc. are mentioned.

As a commercial item of a radiation sensitive radical polymerization initiator, for example, IRGACURE-124, copper-149, copper-184, copper-369, copper-500, copper-651, copper-819, copper-907, copper-1000, copper- 1700, East-1800, East-1850, East-2959, Darocur-1116, East-1173, East-1664, East-2959, East-4043 (above, made by Ciba Specialty Chemicals), KAYACURE-DETX, East -MBP, copper-DMBI, copper-EPA, copper-OA (above, manufactured by Nippon Kayaku Co., Ltd.), LUCIRIN TPO (manufactured by BASF Corporation), VICURE-10, copper-55 (above, manufactured by STAUFFER Corporation), TRIGONALP1 (Made by AKZO), SANDORAY 1000 (manufactured by SANDOZ), DEAP (manufactured by APJOHN), QUANTACURE-PDO, copper-ITX, copper-EPD (above, manufactured by WARD BLEKINSOP), and the like.

These (C) radiation sensitive polymerization initiators can be used individually or in mixture of 2 or more types.

The usage-amount of the (C) radiation sensitive polymerization initiator in a 1st composition becomes like this. Preferably it is 1-40 weight part with respect to 100 weight part of (A) polymer, More preferably, it is 3 to 35 weight part. (C) When the usage-amount of a radiation sensitive polymerization initiator is less than 1 weight part, the heat resistance, surface hardness, and chemical resistance of the cured film obtained may fall, and when it exceeds 40 weight part, there exists a tendency for transparency to fall.

In 1st composition, it is also possible to obtain the highly sensitive radiation-sensitive curable resin composition with little inactivation by oxygen in air by using together (C) a radiation sensitive sensitizer together with 1 or more types of radiation sensitizers.

As such a radiation sensitive sensitizer, N-methyl diethanolamine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, ethyl p-dimethylamino benzoate, for example and p-dimethylaminobenzoic acid i-amyl, 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid and the like. Of these sensitizers, 4,4'-bis (diethylamino) benzophenone or 2,4-diethyl thioxanthone is preferred.

These radiation sensitizers can also use 2 or more types simultaneously.

The use ratio of the radiation sensitive sensitizer is preferably 40 parts by weight or less, and more preferably 20 parts by weight or less based on 100 parts by weight of the (C) radiation sensitive polymerization initiator. When the use ratio of a radiation sensitive sensitizer exceeds 40 weight part, developing residues may become easy to produce.

In addition to the above-mentioned (A) polymer, (B) polymerizable unsaturated compound, and (C) radiation sensitive polymerization initiator, a 1st composition can contain arbitrary additives other than the above as needed in the range which does not impair the effect of this invention. have. As such an optional additive, an adhesion | attachment adjuvant, surfactant, a storage stabilizer, a heat resistance improving agent, etc. can be mix | blended, for example.

The said adhesion | attachment adjuvant is a component which can be used in order to improve the adhesiveness of the cured film obtained and a board | substrate.

As such an adhesion | attachment adjuvant, the functional silane coupling agent which has reactive functional groups, such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, an epoxy group, is preferable, The trimethoxysilyl benzoic acid, (gamma) -methacryloxypropyl trimethoxy as an example thereof Silane, vinyltriacetoxysilane, vinyltrimethoxysilane, isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane and the like.

These adhesion aids can be used individually or in mixture of 2 or more types.

The compounding quantity of an adhesion | attachment adjuvant becomes like this. Preferably it is 20 weight part or less with respect to 100 weight part of (A) polymers, More preferably, it is 15 weight part or less. When the compounding quantity of an adhesion | attachment adjuvant exceeds 20 weight part, it may become easy to produce a development residue.

The said surfactant is a component which can be used in order to improve applicability | paintability.

As such surfactant, a fluorochemical surfactant, silicone type surfactant, etc. are preferable, for example.

As said fluorine-type surfactant, the compound which has a fluoroalkyl group and / or a fluoroalkylene group in at least any part of a terminal, a main chain, and a side chain is preferable, As an example, 1,1,2,2- tetrafluoro-n-octyl ( 1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di (1,1,2 , 2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1, 2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, perfluoro-n-dodecanesulfonic acid Sodium, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane Or sodium fluoroalkylbenzenesulfonate, sodium fluoroalkyl phosphate, sodium fluoroalkyl carboxylate, diglycerine tetrakis Fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, other fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, carboxylic acid Fluoroalkyl esters and the like.

As a commercial item of a fluorine-type surfactant, BM-1000, BM-1100 (above, BM CHEMIE company make), Megapack F142D, copper F172, copper F173, copper F183, copper F178, copper F191, copper F471, copper F476 (Above, Dai Nippon Ink Chemical Industries, Ltd.), Florade FC-170C, East-171, East-430, East-431 (above, Sumitomo 3M Co., Ltd.), Suflon S-112, Dong-113, East-131, East-141, East-145, East-382, Suflon SC-101, East-102, East-103, East-104, East-105, East-106 (above, Asahi Glass (Production) Co., Ltd.), F-top EF301, copper 303, copper 352 (above, Shinsei Kasei Co., Ltd.), Pgentant FT-100, copper-110, copper-140A, copper-150, copper-250, copper -251, copper-300, copper-310, copper-400S, pgentant FTX-218, copper-251 (above, manufactured by Neos), etc. are mentioned.

As said silicone type surfactant, Toray silicon DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ-6032, copper SF-8428 , DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicon Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (more Commercially available, such as GE Toshiba Silicone Co., Ltd., may be mentioned.

Moreover, as surfactant other than the above, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene-n-octylphenyl ether and polyoxyethylene-n-nonylphenyl ether; Nonionic surfactant, such as polyoxyethylene dialkyl ester, such as polyoxyethylene dilaurate and polyoxyethylene distearate, organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), (meth) acryl Acid copolymer polyflow N0.57, copper N0.95 (above, Kyoesha Chemical Co., Ltd. product) etc. are mentioned.

These surfactant can be used individually or in mixture of 2 or more types.

The blending amount of the surfactant is preferably 1.0 part by weight or less, and more preferably 0.5 part by weight or less based on 100 parts by weight of the polymer (A). In this case, when the compounding quantity of surfactant exceeds 1.0 weight part, film nonuniformity may arise easily.

Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and the like, and more specifically 4-methoxyphenol and N-nitroso-N-phenyl Hydroxylamine aluminum etc. are mentioned.

These storage stabilizers can be used individually or in mixture of 2 or more types.

The compounding quantity of a storage stabilizer becomes like this. Preferably it is 3.0 weight part or less with respect to 100 weight part of (A) polymers, More preferably, it is 0.5 weight part or less. In this case, when the compounding quantity of a storage stabilizer exceeds 3.0 weight part, there exists a possibility that a sensitivity may fall and a pattern shape may deteriorate.

Examples of the heat resistance improver include N- (alkoxymethyl) glycoluril compounds, N- (alkoxymethyl) melamine compounds, compounds having two or more oxiranyl groups, and the like.

Examples of the N- (alkoxymethyl) glycoluril compound include N, N, N ', N'-tetra (methoxymethyl) glycoluril, N, N, N', N'-tetra (ethoxymethyl) Glycoluril, N, N, N ', N'-tetra (n-propoxymethyl) glycoluril, N, N, N', N'-tetra (i-propoxymethyl) glycoluril, N, N, N ', N'-tetra (n-butoxymethyl) glycoluril, N, N, N', N'-tetra (t-butoxymethyl) glycoluril and the like.

Among these N- (alkoxymethyl) glycoluril compounds, N, N, N ', N'-tetra (methoxymethyl) glycoluril is preferable.

Examples of the N- (alkoxymethyl) melamine compound include N, N, N ', N', N ", N" -hexa (methoxymethyl) melamine, N, N, N ', N', N " , N "-hexa (ethoxymethyl) melamine, N, N, N ', N', N", N "-hexa (n-propoxymethyl) melamine, N, N, N ', N', N" , N "-hexa (i-propoxymethyl) melamine, N, N, N ', N', N", N "-hexa (n-butoxymethyl) melamine, N, N, N ', N', N ", N" -hexa (t-butoxymethyl) melamine, etc. are mentioned.

Among these N- (alkoxymethyl) melamine compounds, N, N, N ', N', N ", N" -hexa (methoxymethyl) melamine is preferable, and as its commercial item, for example, Nicarac N-2702 And MW-30M (above, Sanwa Chemical Co., Ltd.).

Examples of the compound having two or more oxiranyl groups include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol. Diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol digly Cylyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, etc. are mentioned.

As a commercial item of the compound which has two or more oxiranyl groups, for example, epolite 40E, copper 100E, copper 200E, copper 70P, copper 200P, copper 400P, copper 1500NP, copper 80MF, copper 100MF, copper 1600, copper 3002, copper 4000 (above, Kyoesha Chemical Co., Ltd. product) etc. are mentioned.

These heat resistance improvers can be used individually or in mixture of 2 or more types.

The first composition is prepared by uniformly mixing the (A) polymer, (B) polymerizable unsaturated compound and (C) radiation sensitive polymerization initiator and other components optionally added. The first composition is preferably dissolved in a suitable solvent and used in solution. For example, the radiation-sensitive resin composition in a solution state by mixing (A) a polymer, (B) a polymerizable unsaturated compound and (C) a radiation-sensitive polymerization initiator and other components optionally added in a predetermined ratio in a suitable solvent. Can be prepared.

As a solvent used for manufacture of a 1st composition, each component of (A) a polymer, (B) a polymerizable unsaturated compound, and (C) a radiation sensitive polymerization initiator and the other components arbitrarily mix | blended is melt | dissolved uniformly, and each component It is used that does not react with.

As such a solvent, the same thing as what was illustrated as a solvent which can be used in order to manufacture the above-mentioned (A) polymer is mentioned.

Among these solvents, for example, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters, and diethylene glycol are preferably used in view of solubility of each component, reactivity with each component, ease of coating film formation, and the like. Among these, for example, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethylmethyl Ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate and ethyl ethoxypropionate can be particularly preferably used.

Moreover, a high boiling point solvent can also be used together with the said solvent. By using an appropriate amount of high boiling point solvent together, the effect which raises in-plane uniformity of a film thickness can be anticipated. As a high boiling point solvent which can be used together, it is N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpi, for example. Ralidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, male Diethyl acid, gamma -butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like. Of these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

When using a high boiling point solvent together as a solvent of a 1st composition, the usage-amount is 50 weight% or less with respect to solvent whole quantity, More preferably, it is 40 weight% or less, More preferably, it is 30 weight% or less. When the usage-amount of a high boiling point solvent exceeds this usage-amount, the film thickness uniformity, a sensitivity, and a residual film ratio of a coating film may fall.

When the first composition is prepared in a solution state, a component other than the solvent occupying in the solution, namely (A) polymer, (B) polymerizable unsaturated compound and (C) radiation-sensitive polymerization initiator and other components optionally added The ratio of the total amount can be arbitrarily set depending on the purpose of use, the value of the desired film thickness, or the like, and can be, for example, 5 to 80% by weight, but the preferred value depends on the method of using the first composition solution. This will be described later.

The composition solution thus prepared may be used after being filtered using a Millipore filter, a membrane filter, or the like having a pore size of about 0.5 μm.

<2nd composition>

The second composition is preferably a radiation sensitive resin composition containing (A) a polymer and (D) 1,2-quinonediazide compound.

Preferred specific examples of the polymer (A) used in the second composition include, for example, methacrylic acid / styrene / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / glycidyl methacrylate / Tetrahydrofurfuryl methacrylate copolymer, methacrylic acid / styrene / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / glycidyl methacrylate / p-vinylbenzyl glycidyl ether Tetrahydrofurfuryl methacrylate copolymer, methacrylic acid / styrene / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / glycidyl methacrylate / polyethylene glycol monomethacrylate aerial Copolymer, methacrylic acid / styrene / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / glycidyl methacrylate / polypropylene glycol monomethacrylate copolymer; and the like.

(D) 1,2-quinonediazide compound used for a 2nd composition is a 1,2-quinonediazide compound which produces | generates a carboxylic acid by irradiation of a radiation, and is a phenolic compound or an alcoholic compound (Hereinafter, a "nucleus" ) And 1,2-naphthoquinone diazide sulfonic acid halide can be used.

Examples of the mother core include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother cores.

As these specific examples, As trihydroxy benzophenone, For example, 2,3, 4- trihydroxy benzophenone, 2,4, 6- trihydroxy benzophenone etc .;

As tetrahydroxybenzophenone, for example, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'- Tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone and the like;

As pentahydroxy benzophenone, For example, 2,3,4,2 ', 6'- pentahydroxy benzophenone etc .;

As hexahydroxybenzophenone, for example, 2,4,6,3 ', 4', 5'hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone Etc;

As (polyhydroxyphenyl) alkanes, for example, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1 -Tri (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3 -Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] Ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5 , 6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan and the like;

As other parent nuclei, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 2- [bis {(5- Isopropyl-4-hydroxy-2-methyl) phenyl} methyl], 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl ) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene, etc. are mentioned, respectively.

Moreover, the 1, 2- naphthoquinone diazide sulfonic acid amides which changed the ester bond of the above-mentioned mother-nucleus into an amide bond, for example, 2,3, 4- trihydroxy benzophenone-1, 2-naphthoquinone Diazide-4-sulfonic acid amide etc. can also be used preferably.

Of these mother cores, 2,3,4,4'-tetrahydroxybenzophenone or 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethyl Suede] bisphenol is preferred.

As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable, and specific examples thereof include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2- Naphthoquinone diazide-5-sulfonic acid chloride is mentioned, Among these, it is preferable to use 1,2-naphthoquinone diazide-5-sulfonic acid chloride.

In the condensation reaction, 1,2-naphthoquinonediazide sulfonic acid halide, which is preferably 30 to 85 mol%, more preferably 50 to 70 mol%, based on 1 equivalent of the OH group in the phenolic compound or the alcoholic compound. Can be used.

The condensation reaction can be carried out by a known method.

(D) 1,2-quinonediazide compound can be used individually or in combination of 2 or more types.

The use ratio of the (D) 1,2-quinonediazide compound is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight based on 100 parts by weight of the polymer (A). When this ratio is less than 5 parts by weight, the difference in solubility between the irradiated portion and the unirradiated portion of the radiation in the alkaline aqueous solution serving as the developing solution is small, and patterning may be difficult, and the heat resistance and solvent resistance of the resulting cured film may be difficult. It may become insufficient. On the other hand, when this ratio exceeds 100 weight part, the solubility to the said aqueous alkali solution in a radiation part may become inadequate and it may become difficult to develop.

The second composition contains the above (A) polymer and (D) 1,2-quinonediazide compound, and if necessary, (B) a polymerizable unsaturated compound, a thermosensitive acid generator, an epoxy resin, an adhesion aid, Surfactant and the like.

The said (B) polymerizable unsaturated compound is the same as that mentioned above as a preferable structural component of a 1st composition. However, the usage-amount of the (B) polymerizable unsaturated compound in a 2nd composition becomes like this. Preferably it is 50 weight part or less, More preferably, it is 30 weight part or less with respect to 100 weight part of (A) polymers.

By containing (B) a polymerizable unsaturated compound in such a ratio, the heat resistance, surface hardness, etc. of the cured film obtained can be improved. When this usage amount exceeds 50 weight part, film roughness may generate | occur | produce in the process of forming the coating film of a composition on a board | substrate.

The said thermosensitive acid generator can be used in order to improve the heat resistance and hardness of the cured film obtained. Specific examples thereof include onium salts such as sulfonium salts (excluding triarylsulfonium salts), benzothiazonium salts, ammonium salts, and phosphonium salts.

Specific examples of the sulfonium salts include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts, and the like.

Specific examples thereof include alkylsulfonium salts, for example 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyl Oxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl- 3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate and the like;

As the benzylsulfonium salt, for example, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexa Fluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro- 4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, etc .;

As the dibenzylsulfonium salt, for example, dibenzyl-4-hydroxyphenylsulfoum hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfoum hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium Hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3- Methyl-4-hydroxy-5-tert-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate and the like;

As the substituted benzylsulfonium salt, for example, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p -Chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4- Hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and the like.

Specific examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzoteazonium tetrafluoroborate, and 3- (p-meth Oxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluororoantimonate, etc. Benzyl benzothiazonium salt is mentioned.

Of these, sulfonium salts or benzothiazonium salts are preferably used, and in particular, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetium Methoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate or 3-benzylbenzothia Zonium hexafluoroantimonate is preferably used.

Examples of these commercially available products include San-Aid SI-L85, SI-L110, SI-L145, SI-L150, and SI-L160 (above, manufactured by Sanshin Kagaku Kogyo Co., Ltd.).

The use ratio of the thermosensitive acid generator in a 2nd composition becomes like this. Preferably it is 20 weight part or less, More preferably, it is 5 weight part or less with respect to 100 weight part of (A) polymers. When this usage amount exceeds 20 weight part, precipitates may precipitate in a coating film formation process, and may interrupt the coating film formation.

The epoxy resin is not limited as long as it does not affect compatibility with other components or solvents, but is preferably a bisphenol A epoxy resin, a phenol novolac epoxy resin, a cresol novolac epoxy resin, a cyclic aliphatic epoxy resin, or glycy And a diester ester epoxy resin, a glycidyl amine epoxy resin, a heterocyclic epoxy resin, and a resin (co) polymerized with glycidyl methacrylate. Among these, bisphenol A epoxy resin, cresol novolak-type epoxy resin, glycidyl ester type epoxy resin, and the like are more preferable.

The use ratio of the epoxy resin in a 2nd composition becomes like this. Preferably it is 30 weight part or less with respect to 100 weight part of (A) polymers. By containing an epoxy resin in such a ratio, the heat resistance, surface hardness, etc. of the cured film obtained can be improved further. When this ratio exceeds 30 weight part, when forming the coating film of a composition on a board | substrate, the film thickness uniformity of a coating film may become inadequate.

In addition, when (A) polymer has an oxiranyl group, although (A) polymer can also be called "epoxy resin", (A) polymer differs from the said epoxy resin by the point which has alkali solubility.

As an adhesion | attachment adjuvant and surfactant which a 2nd composition can contain, it is the same as what was mentioned above about the adhesion | attachment adjuvant and surfactant which a 1st composition can contain.

The second composition is prepared by uniformly mixing the (A) polymer and (D) 1,2-quinonediazide compound and other components optionally added. The second composition is preferably dissolved in a suitable solvent and used in solution. For example, the curable resin composition of a solution state can be manufactured by mixing (A) polymer, (D) 1,2-quinonediazide compound, and the other component added arbitrarily at a predetermined ratio in a suitable solvent.

As the solvent used in the preparation of the second composition, those components (A) polymer and (D) 1,2-quinonediazide compound and other components optionally blended are uniformly dissolved and do not react with each component. do. As such a solvent, it is the same as that mentioned above as a solvent which can be used for manufacture of a 1st composition. The proportion of the total amount of components other than the solvent occupied in the composition solution, that is, the (A) polymer and (D) 1,2-quinonediazide compound and other components optionally added may be arbitrarily selected depending on the purpose of use or the value of the desired film thickness. It can be set, for example, 5 to 50 weight%, Preferably it is 10 to 40 weight%, More preferably, it can be 15 to 35 weight%.

The second composition solution may be used after being filtered using a Millipore filter, a membrane filter, or the like having a pore size of about 0.5 μm.

<Third composition>

The third composition is preferably a one-component curable resin composition containing the polymer (A) and the cationic polymerizable compound (E).

Preferable specific examples of the polymer (A) used in the third composition include, for example, glycidyl acrylate / acrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate / styrene copolymer, methacrylic acid Glycidyl / methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene copolymer, methacrylate glycidyl / methacrylic acid / methyl methacrylate / styrene copolymer , Glycidyl methacrylate / methacrylic acid / cyclohexyl acrylate / p-methoxystyrene copolymer, glycidyl acrylate / acrylic acid / N-phenylmaleimide / styrene copolymer, glycidyl methacrylate / methacryl Acid / N-phenylmaleimide / styrene copolymer, glycidyl methacrylate / methacrylic acid / N-cyclohexylmaleimide / styrene copolymer, glycidyl methacrylate / methacrylic acid / tricyclo [5.2. 1.0 ^2,6] decane-8-yl methacrylate / 1,3-butadiene copolymers, methacrylic acid 6,7-oxiranyl Heptyl / methacrylic acid / tricyclo [5.2.1.0 ^2,6] decane-8-yl methacrylate / styrene copolymers, glycidyl methacrylate / methacrylic acid / tricyclo [5.2.1.0 ^2,6] Decan-8-ylmethacrylate / styrene / 1,3-butadiene copolymer, methacrylic acid 6,7-oxyranylheptyl / acrylic acid / maleic anhydride / styrene copolymer, methacrylic acid 6,7-oxyranylheptyl / Acrylic acid / maleic anhydride / methacrylic acid t-butyl copolymer, and the like.

Among these, glycidyl methacrylate / methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / styrene copolymer and glycidyl methacrylate / methacrylic acid are more preferable. / N-phenylmaleimide / styrene copolymer, methacrylate glycidyl / methacrylic acid / N-cyclohexylmaleimide / styrene copolymer, methacrylate glycidyl / methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / 1,3-butadiene copolymer or methacrylate glycidyl / methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / Styrene / 1,3-butadiene copolymer.

The (E) cationically polymerizable compound used for the third composition is a cationically polymerizable compound other than the (A) polymer or (A ') polymer.

The cationic polymerizable compound (E) is not particularly limited as long as it can be polymerized under acidic conditions, but for example, at least one member selected from the group consisting of an oxetane ring skeleton, a 3.4-oxiranylcyclohexyl group and an oxiranyl group can be used. The compound which has group which can react with addition to the oxiranyl group or oxetanyl group which the (A) polymer preferably contains, such as a compound which has two or more in a molecule | numerator, is mentioned.

The following are mentioned as a specific example of such a (C) cationically polymerizable compound.

As a compound having two or more oxetane ring skeletons in a molecule, for example, 3,7-bis (3-oxetanyl) -5-oxanonane, 3,3 '-(1,3- (2-methylenyl) Propanediyl bis (oxymethylene)) bis (3-ethyloxetane), 1,4-bis ((3-ethyl-3-oxetanyl) methoxymethyl) benzene, 1,2-bis ((3-ethyl -3-oxetanyl) methoxymethyl) ethane, 1,3-bis ((3-ethyl-3-oxetanyl) methoxymethyl) propane, ethylene glycol bis ((3-ethyl-3-oxetanyl ) Methyl) ether, dicyclopentenyl bis ((3-ethyl-3-oxetanyl) methyl) ether, triethyleneglycol bis ((3-ethyl-3-oxetanyl) methyl) ether, tetraethyleneglycol bis ((3-ethyl-3-oxetanyl) methyl) ether, tricyclodecanediyldimethylene bis ((3-ethyl-3-oxetanyl) methyl) ether, trimethylolpropane tris ((3-ethyl-3 -Oxetanyl) methyl) ether, 1,4-bis ((3-ethyl-3-oxetanyl) methoxy) butane, 1,6-bis ((3-ethyl-3-oxetanyl) methoxy Hexane, pentaerythritol Lis ((3-ethyl-3-oxetanyl) methyl) ether, pentaerythritol tetrakis ((3-ethyl-3-oxetanyl) methyl) ether, polyethylene glycol bis ((3-ethyl-3-jade Cetanyl) methyl) ether, dipentaerythritol hexakis ((3-ethyl-3-oxetanyl) methyl) ether, dipentaerythritol pentakis ((3-ethyl-3-oxetanyl) methyl) ether, Reaction product of dipentaerythritol tetrakis ((3-ethyl-3-oxetanyl) methyl) ether, dipentaerythritol hexakis ((3-ethyl-3-oxetanyl) methyl) ether and caprolactone, Reaction product of dipentaerythritol pentakis ((3-ethyl-3-oxetanyl) methyl) ether with caprolactone, ditrimethylolpropane tetrakis ((3-ethyl-3-oxetanyl) methyl) ether, Reaction product of bisphenol A bis ((3-ethyl-3-oxetanyl) methyl) ether with ethylene oxide, bisphenol A bis ((3-ethyl-3-oxetanyl) methyl) ether with propylene oxide Generate reaction of , Reaction product of hydrogenated bisphenol A bis ((3-ethyl-3-oxetanyl) methyl) ether with ethylene oxide, hydrogenated bisphenol A bis ((3-ethyl-3-oxetanyl) methyl) ether And reaction products of propylene oxide with bisphenol F bis ((3-ethyl-3-oxetanyl) methyl) ether and ethylene oxide.

As a compound which has 2 or more of 3, 4- oxiranyl cyclohexyl groups in a molecule | numerator, for example, 3, 4- oxiranyl cyclohexylmethyl-3 ', 4'- oxiranyl cyclohexane carboxylate, 2- (3 , 4-Oxiranylcyclohexyl-5,5-spiro-3,4-oxyranyl) cyclohexane-meta-dioxane, bis (3,4-oxyranylcyclohexylmethyl) adipate, bis (3,4- Oxiranyl 6-methylcyclohexylmethyl) adipate, 3,4-oxyranyl 6-methylcyclohexyl-3 ', 4'-oxiranyl 6'-methylcyclohexanecarboxylate, methylenebis (3,4-oxy Ranylcyclohexane), dicyclopentadiene diepoxide, ethylene glycol bis (3,4-oxyranylcyclohexylmethyl) ether, ethylenebis (3,4-oxyranylcyclohexanecarboxylate), lactone modified 3,4 -Oxiranylcyclohexylmethyl-3 ', 4'- oxiranylcyclohexanecarboxylate, etc. are mentioned.

As a compound which has two or more oxiranyl groups in a molecule | numerator, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogen Of bisphenol compounds such as added bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S diglycidyl ether Diglycidyl ether;

1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol digly Polyglycidyl ethers of polyhydric alcohols such as cydyl ether;

Polyglycidyl ethers of polyether polyols obtained by the reaction of aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin with one or two or more alkylene oxides;

Epoxy resins such as phenol novolac type epoxy resins, cresol novolac type epoxy resins, polyphenol type epoxy resins, and cyclic aliphatic epoxy resins; Diglycidyl esters of aliphatic long chain dibasic acids;

In addition to polyglycidyl ester of a higher polyhydric fatty acid, oxyranylated soybean oil, oxyranylated linseed oil, etc. are mentioned.

As a commercial item of the compound which has two or more oxiranyl groups in a molecule | numerator, Eporite 100MF (made by Kyoesha Chemical Co., Ltd.), Epiol TMP (Nippon Yushi Co., Ltd.) as a polyglycidyl ether of a polyhydric alcohol, for example. Produce);

Epicoat 828, copper 1001, copper 1002, copper 1003, copper 1004, copper 1007, copper 1009, copper 1010 (above, manufactured by Yuka Shell Epoxy Co., Ltd.) and the like as bisphenol A epoxy resin;

As bisphenol F-type epoxy resin, Epicoat 807 (made by Yuka Shell Epoxy Co., Ltd.) etc .;

As a phenol novolak-type epoxy resin, Epicoat 152, Copper 154, Copper 157S65 (above, manufactured by Yuka Shell Epoxy), DPPN201, Copper 202 (above, manufactured by Nippon Kayaku Co., Ltd.), etc .;

As a cresol novolak-type epoxy resin, DOCN102, 103S, 104S, 1020, 1025, 1027 (above, Nippon Kayaku Co., Ltd. make), Epicoat 180S75 (Yukaka Shell Epoxy Co., Ltd.), etc .;

As a polyphenol type epoxy resin, Epicoat 1032H60, Copper XY-4000 (above, Yuka Shell Epoxy Co., Ltd. product) etc. are mentioned;

As the cyclic aliphatic epoxy resin, CY-175, copper 177, copper 179, araldite CY-182, copper 192, copper 184 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), DRL-4221, copper 4206, 4234, copper 4299 (above, manufactured by UCC Corporation), Shodyne 509 (manufactured by Showa Denko Co., Ltd.), epiclon 200, copper 400 (more, manufactured by Dainippon Ink, Co., Ltd.), epicoat 871, copper 872 (Even above, Yuka Shell Epoxy Co., Ltd. product), DD-5661, copper 5662 (above, Serrano Coating Co., Ltd. product), etc. are mentioned, respectively.

Among these (E) cationically polymerizable compounds, phenol novolak type epoxy resins, polyphenol type epoxy resins, and the like are preferable.

In the present invention, the (E) cationically polymerizable compound may be used alone or in combination of two or more thereof.

The use ratio of the (E) cationically polymerizable compound in the third composition is preferably 3 to 100 parts by weight, more preferably 3 to 100 parts by weight of (E) the cationically polymerizable compound to 100 parts by weight of the polymer (A) 5 to 50 parts by weight.

In the 3rd composition, the cured film which has sufficient surface hardness can be obtained by making the usage-amount of the (E) cationically polymerizable compound into the said range. The third composition is particularly excellent in long term storage stability.

It is preferable that a 3rd composition contains (F) hardening | curing agent or (G) acid generator further in addition to the said (A) polymer and (E) cationically polymerizable compound, and can contain an adhesion | attachment adjuvant, surfactant, etc. as needed. have.

The (F) hardener which the 3rd composition can contain is a compound which has 1 or more types of functional groups which can react with the oxiranyl group or oxetanyl group which (A) polymer contains preferably.

As such a (F) hardening | curing agent, a copolymer of polyhydric carboxylic acid, polyhydric carboxylic anhydride, unsaturated polyhydric carboxylic anhydride, and another olefinic unsaturated compound (however, two or more oxiranyl groups or oxetanyl groups And the like, hereinafter, referred to as "carboxylic acid anhydride group-containing copolymer", and the like.

As said polyhydric carboxylic acid, aliphatic polyhydric carboxylic acid, alicyclic polyhydric carboxylic acid, aromatic polyhydric carboxylic acid, etc. are mentioned, for example. As aliphatic polyhydric carboxylic acid, For example, succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, itaconic acid, etc .;

As alicyclic polyhydric carboxylic acid, For example, hexahydrophthalic acid, a 1, 2- cyclohexane dicarboxylic acid, a 1, 2, 4- cyclohexane tricarboxylic acid, a cyclopentane tetracarboxylic acid, etc .;

Examples of the aromatic polyvalent carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 1,2,5,8-naphthalene tetracarboxylic acid, and the like. Among these polyhydric carboxylic acids, aromatic polyhydric carboxylic acids are preferable from the viewpoints of reactivity, heat resistance of the cured film formed, and the like.

As said polyhydric carboxylic anhydride, aliphatic dicarboxylic acid anhydride, alicyclic polyhydric carboxylic dianhydride, aromatic polyhydric carboxylic anhydride, ester group containing acid anhydride, etc. are mentioned, for example. As said aliphatic dicarboxylic acid anhydride, itaconic anhydride, succinic anhydride, citraconic acid anhydride, dodecenyl succinic anhydride, tricarvanic acid anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Anhydrous acid and the like;

As an alicyclic polyhydric carboxylic dianhydride, For example, 1,2,3,4- butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, etc .;

As aromatic polyhydric carboxylic anhydride, For example, phthalic anhydride, a pyromellitic dianhydride, trimellitic anhydride, a benzophenone tetracarboxylic acid anhydride etc .;

As ester group containing acid anhydride, ethylene glycol bis anhydride trimellitate, glycerin tris anhydride trimellitate, etc. are mentioned, for example. Among these polyhydric carboxylic anhydrides, aromatic polyhydric carboxylic anhydrides are preferable, and trimellitic anhydride is particularly preferable in that a protective film having high heat resistance can be obtained.

As unsaturated polyhydric carboxylic anhydride in the said carboxylic acid anhydride group containing copolymer, For example, maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrahydrophthalic anhydride Etc. can be mentioned. These unsaturated polyhydric carboxylic anhydrides can be used individually or in mixture of 2 or more types.

As another olefinic unsaturated compound, For example, styrene, p-methylstyrene, p-methoxy styrene, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate , N-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, N- Phenyl maleimide, N-cyclohexyl maleimide, etc. are mentioned. These other olefinically unsaturated compounds can be used individually or in mixture of 2 or more types.

As a preferable specific example of a carboxylic acid anhydride group containing copolymer, For example, maleic anhydride / styrene copolymer, citraconic anhydride / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate copolymer, etc. Can be mentioned.

The copolymerization ratio of the unsaturated polyhydric carboxylic anhydride in the carboxylic acid anhydride group-containing copolymer is preferably 1 to 80% by weight, more preferably 10 to 60% by weight. By using the copolymer of such a copolymerization ratio, the cured film excellent in the planarization ability can be obtained.

The Mw of the carboxylic acid anhydride group-containing copolymer is preferably 500 to 50,000, more preferably 500 to 10,000. By using the copolymer of such a molecular weight range, the cured film excellent in the planarization ability can be obtained.

Said (F) hardening | curing agent can be used individually or in mixture of 2 or more types.

The use ratio of the (F) curing agent in the third composition is the amount of the (F) curing agent to 100 parts by weight of the polymer (A), preferably 100 parts by weight or less, more preferably 1 to 80 parts by weight. More preferably, it is 10-60 weight part.

By making the usage-amount of the (F) hardening | curing agent into the said range in a 3rd composition, the flatness of the cured film obtained can be improved more, without impairing the long-term stability of a composition.

The acid generator (G) which the third composition may contain is preferably a compound which generates an acid by irradiation of radiation or a compound which generates an acid by heating. Among these, the former is called a "radiation sensitive acid generator", and the latter is called a "sensitivity acid generator".

As a radiation sensitive acid generator, a diaryl iodonium salt, a triaryl sulfonium salt, a diaryl phosphonium salt, etc. are mentioned, for example.

Examples of the diaryl iodonium salts include diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluorophosphonate, diphenyl iodonium hexafluoroarsenate, and diphenyl iodonium. Trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium p-toluenesulfonate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium Hexafluorophosphonate, 4-methoxyphenylphenyl iodonium Hexafluoroarsenate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium trifluor Low acetate, 4-methoxyphenylphenyl iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoro Arsenate, bis (4-t-part Phenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, etc. are mentioned. have. Among these diaryl iodonium salts, diphenyl iodonium hexafluorophosphonate is particularly preferable.

Examples of the triarylsulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, and triphenylsulfonium trifluoromethanesulfo. Nitrate, Triphenylsulfonium trifluoroacetate, triphenylsulfonium p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate , 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxy Methoxyphenyldiphenylsulfonium p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenyl hexafluorophosphonate, 4-phenylthiophenyldiphenyl Safluoro arsenate, 4-phenylthio phenyl diphenyl trifluoromethanesulfonate, 4-phenylthio phenyl diphenyl trifluoro acetate, 4-phenyl thiophenyl diphenyl p-toluenesulfonate, etc. are mentioned. have. Among these triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate is particularly preferable.

As said diaryl phosphonium salt, (1-6- (eta)-cumene) ((eta) -cyclopentadienyl) iron hexafluoro phosphonate etc. are mentioned, for example.

As a commercial item of a radiation sensitive acid generator, as a diaryliodonium salt, it is UVI-6950, UVI-6970, UVI-6974, UVI-6990 (above, Union Carbide company make), MPI-103, BBI-103 ( Above, Midori Kagaku Co., Ltd. product);

As a triarylsulfonium salt, for example, Adeka Optomer SP-150, Adeka Optomer SP-151, Adeka Optomer SP-170, Adeka Optomer SP-171 (above, manufactured by Asahi Denka Kogyo Co., Ltd.) , CI-2481, CI-2624, CI-2639, CI-2064 (above, Nihon Soda Co., Ltd.), DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103 (Above, manufactured by Midori Chemical Co., Ltd.), CD-1010, CD-1011, CD-1012 (above, manufactured by Satomer Co., Ltd.), and the like;

Examples of the diaryl phosphonium salt include Irgacure 261 (manufactured by Ciba Specialty Chemicals Co., Ltd.); PCI-061T, PCI-062T, PCI-020T, PCI-022T (above, Nippon Kayaku Co., Ltd.), etc. are mentioned, respectively.

Among these commercial items, the cured film obtained by UVI-6970, UVI-6974, UVI-6990, Adeka Optomer SP-170, Adeka Optomer SP-171, CD-1012, MPI-103, etc. has high surface hardness. It is preferable at the point which has.

The radiation sensitive acid generators may be used alone or in combination of two or more thereof.

As a thermosensitive acid generator which a 3rd composition can contain, the thing of the same kind as the thermosensitive acid generator which a said 2nd composition can contain is mentioned.

The use ratio of the (G) acid generator in a 3rd composition is the usage-amount of the (G) acid generator with respect to 100 weight part of (A) polymers, Preferably it is 20 weight part or less, More preferably, it is 0.05- 20 parts by weight, more preferably 0.1 to 10 parts by weight.

As an adhesion | attachment adjuvant and surfactant which a 3rd composition can contain, it is the same as what was mentioned above about the adhesion | attachment adjuvant and surfactant which a 1st composition can contain. However, the quantity of the adhesion | attachment adjuvant which a 3rd composition can contain is preferably 30 weight part or less with respect to 100 weight part of (A) polymers, More preferably, it is 25 weight part or less. When this value exceeds 30 weight part, the heat resistance of the cured film obtained may become inadequate. The amount of the surfactant that the third composition may contain is preferably 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the polymer (A). When this value exceeds 5 weight part, film nonuniformity may arise easily.

The third composition is prepared by uniformly mixing the above-mentioned (A) polymer and (E) cationically polymerizable compound and other components optionally added. The third composition is preferably dissolved in a suitable solvent and used in solution. For example, the radiation sensitive resin composition of a solution state can be manufactured by mixing (A) polymer, (E) cationically polymerizable compound, and the other component added arbitrarily in a predetermined ratio.

As a solvent used for manufacture of a 3rd composition, what dissolves each component of (A) polymer, (E) cationically polymerizable compound, and the other component arbitrarily mix | blended uniformly, and does not react with each component is used. As such a solvent, it is the same as that mentioned above as a solvent which can be used for manufacture of a 1st composition. The ratio of the total amount of components other than the solvent occupied in the composition solution, that is, the (A) polymer and the (E) cationic polymerizable compound and other components optionally added can be arbitrarily set according to the purpose of use or the value of the desired film thickness, etc., For example, it may be 1 to 50 weight%, Preferably it is 5 to 40 weight%.

The third composition solution may be used after being filtered using a Millipore filter, a membrane filter, or the like having a pore size of about 0.5 μm.

<4th composition>

The fourth composition contains the (A ') polymer and the (E) cationically polymerizable compound. The fourth composition is preferably a one-component curable resin composition in which the (A) polymer in the third composition is replaced with the (A ') polymer.

The polymer (A ') used in the fourth composition is preferably the above (A'1) polymer or (A'2) polymer.

As a preferable specific example of the (A'1) polymer which can be used for a 4th composition, For example, glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / tricyclo [5.2.1.0 ^2,6 ] Deccan-8-ylmethacrylate / styrene copolymer, glycidyl methacrylate / methacrylate tetrahydro-2H-pyran-2-yl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmetha Acrylate / styrene copolymer, glycidyl methacrylate / tetrahydroacrylate-2H-pyran-2-yl / N-phenylmaleimide / styrene copolymer, glycidyl methacrylate / tetrahydro-2H methacrylate -Pyran-2-yl / N-phenylmaleimide / styrene copolymer, glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer, methacrylic acid Glycidyl / methacrylic acid tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer, glycidyl methacrylate / acrylic acid 1- ( Cyclohexyloxy) ethyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene copolymer, glycidyl methacrylate / methacrylic acid 1- (cyclohexyloxy) ethyl / Tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene copolymer, glycidyl methacrylate / acrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene air Copolymer, glycidyl methacrylate / methacrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer, glycidyl methacrylate / 2,3-di (tetrahydropyran- 2-yloxycarbonyl) -5-norbornene / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene copolymer, glycidyl / 2,3-di (methacrylate) Tetrahydropyran-2-yloxycarbonyl) -5-norbornene / N-cyclohexylmaleimide / styrene copolymer, glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / tricycloacrylate [5.2.1.0 ^2,6] Kan-8-yl methacrylate / 1,3-butadiene copolymers, glycidyl methacrylate / methacrylic acid tetrahydro -2H- pyran-2-yl / a tree Sickle [5.2.1.0 ^2,6] decane -8-yl methacrylate / 1,3-butadiene copolymer, glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / methyl methacrylate / styrene copolymer, glycidyl methacrylate / Methacrylate tetrahydro-2H-pyran-2-yl / methyl methacrylate / styrene copolymer, glycidyl methacrylate / tetrahydro-2H-pyran-2-yl acrylate / cyclohexyl acrylate / p-meth Oxystyrene copolymer,

Glycidyl methacrylate / methacrylic acid tetrahydro-2H-pyran-2-yl / cyclohexyl acrylate / p-methoxystyrene copolymer, glycidyl acrylate / t-butyl / N-phenylmaleimide / Styrene copolymer, glycidyl methacrylate / t-butyl methacrylate / N-cyclohexylmaleimide / styrene copolymer, methacrylic acid 6,7-oxyranylheptyl / tetrahydro-2H-pyran-2 -Yl / methacrylic acid t-butyl / maleic anhydride copolymer, methacrylic acid 6,7-oxyranylheptyl / methacrylate tetrahydro-2H-pyran-2-yl / methacrylate t-butyl / maleic anhydride Acid copolymer, methacrylic acid 6,7-oxiranylheptyl / methacrylate t-butyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene copolymer, methacrylic acid 6, 7-Oxiranylheptyl / methacrylic acid t-butyl / maleic anhydride / styrene copolymer, 1- (cyclohexyloxy) ethyl / tricyclo [5.2.1.0 ^2,6 ] decane methacrylate glycidyl / acrylic acid -8-ylmethacrylate / styrene / 1,3-butadiene copolymer, glycidyl methacrylate / methacrylic acid 1- (cyclohexyloxy) ethyl / tricyclo [5.2.1.0 ^2,6 ] decane- 8-ylmethacrylate / styrene / 1,3-butadiene copolymer etc. are mentioned.

Of these, more preferably glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / styrene copolymer, meta Glycylate Glycidyl / Methacrylic Acid Tetrahydro-2H-pyran-2-yl / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / styrene copolymer, Glycidyl Methacrylic Acid / Tetrahydro-2H-pyran-2-yl / N-phenylmaleimide / styrene copolymer, methacrylate glycidyl / methacrylate tetrahydro-2H-pyran-2-yl / N-phenylmaleimide / styrene Copolymer, glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer, glycidyl methacrylate / tetrahydro-2H-pyran- 2-yl / N-cyclohexylmaleimide / styrene copolymer, glycidyl methacrylate / acrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene Polymer, glycidyl methacrylate / methacrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer, glycidyl methacrylate / 2,3-di (tetrahydropyran- 2-yloxycarbonyl) -5-norbornene / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene copolymer, glycidyl / 2,3-di (methacrylate) Tetrahydropyran-2-yloxycarbonyl) -5-norbornene / N-cyclohexylmaleimide / styrene copolymer or glycidyl methacrylate / t-butyl methacrylate / N-cyclohexyl maleimide / Styrene copolymer.

As a preferable specific example of the (A'2) polymer which can be used for a 4th composition, For example, glycidyl acrylate / styrene copolymer, glycidyl methacrylate / styrene copolymer, glycidyl / tricyclo acrylate [5.2] .1.0 ^2,6 ] decane-8-yl methacrylate copolymer, glycidyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate copolymer, methacrylic acid 6 , 7-Oxiranylheptyl / styrene copolymer, glycidyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate / styrene copolymer, glycidyl methacrylate / N- Phenylmaleimide / styrene copolymer, glycidyl methacrylate / N-cyclohexylmaleimide / styrene copolymer, methacrylic acid 6,7-oxyranylheptyl / tricyclo [5.2.1.0 ^2,6 ] decane-8 -Yl methacrylate copolymer, methacrylic acid 6,7-oxiranylheptyl / N-cyclohexylmaleimide / styrene copolymer, etc. are mentioned.

Among these, More preferably, methacrylate glycidyl / styrene copolymer, methacrylate glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate copolymer, and methacrylate Cydyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / styrene copolymer or glycidyl methacrylate / N-cyclohexylmaleimide / styrene copolymer.

About matters other than the (A ') polymer which concerns on a 4th composition, it can apply as it is what was mentioned above about a 3rd composition as it is, or after adding the obvious change to a person skilled in the art.

<Fifth Composition>

A 5th composition is a two-component curable resin composition which consists of a 1st liquid containing a (A ') polymer and (E) cationically polymerizable compound, and a 2nd liquid containing (F) hardening | curing agent. It is preferable that the 1st liquid of a 5th composition does not contain the (F) hardening | curing agent and the (G) acid generator.

As (A ') polymer used here, it is preferable that it is (A'2) polymer. About the (A'2) polymer which the 1st liquid of a 5th composition can contain, it is the same as that of the above-mentioned as (A'2) superposition | polymerization which can be used for a 4th composition. In addition, about the (E) cationically polymerizable compound which the 1st liquid of a 5th composition can contain, it is the same as that mentioned above as (E) cationically polymerizable compound which can be used for a 3rd composition.

The use ratio of the (E) cationically polymerizable compound in the first liquid of the fifth composition is preferably 3 to 100 parts by weight as the amount of the (E) cationically polymerizable compound to 100 parts by weight of the polymer (A'2). It is more preferably 5 to 50 parts by weight.

The 1st liquid of a 5th composition can contain an adhesion | attachment adjuvant, surfactant, etc. as needed other than the said (A'2) polymer and (E) cationically polymerizable compound.

About an adhesion | attachment adjuvant and surfactant, it is the same as that mentioned above about the adhesion | attachment adjuvant and surfactant which a 3rd composition can contain.

The first liquid of the fifth composition is preferably dissolved in a suitable solvent and used in solution.

As a solvent used for preparation of the 1st liquid of a 5th composition, it is a thing which melt | dissolves each component of (A) polymer and (E) cationically polymerizable compound, and the other components arbitrarily blended uniformly, and does not react with each component. Used. As such a solvent, it is the same as that mentioned above as a solvent which can be used for manufacture of a 1st composition. The ratio of the total amount of components other than the solvent occupied in the composition solution, that is, the (A) polymer and the (E) cationically polymerizable compound and other components optionally added can be arbitrarily set according to the purpose of use, the value of the desired film thickness, or the like, For example, it can be 5 to 75 weight%, Preferably it is 10 to 50 weight%.

The first liquid of the fifth composition solution may be used after being filtered using a Millipore filter, a membrane filter, or the like having a pore size of about 0.5 µm.

The second liquid of the fifth composition is preferably a solution containing the (F) curing agent. As a kind of (F) hardening | curing agent contained in the 2nd liquid of a 5th composition, it is the same as that mentioned above as (F) hardening | curing agent which a 3rd composition can contain.

The solvent which can be used for manufacture of the 2nd liquid of a 5th composition is the same as that mentioned above as a solvent which can be used for manufacture of a 1st composition.

The concentration of the (F) curing agent in the second liquid of the fifth composition is preferably 1 to 80% by weight, more preferably 10 to 60% by weight.

The second liquid of the fifth composition solution may be used after being filtered using a Millipore filter, a membrane filter, or the like having a pore size of about 0.5 μm.

<< forming method of hardened film >>

The method of forming a cured film using the said 1st-5th composition is described below. The first composition is preferably used for forming a spacer of the liquid crystal display device, the second composition for forming an interlayer insulating film or microlens, and the third to fifth compositions for forming a protective film, respectively.

<Method of Forming Spacer Using First Composition>

The method of forming the spacer of a liquid crystal display element using a 1st composition performs the following process (1)-(4) in the order described below.

(1) forming a film of the first composition on a substrate;

(2) exposing radiation to at least a portion of the film;

(3) developing the film after exposure, and

(4) The process of heating the film after image development.

Hereinafter, each of these steps will be described in order.

(1) Process of forming film of 1st composition on board | substrate

First, the film of the composition of the solution of a 1st composition is formed on a board | substrate.

As a board | substrate used for this method, the transparent substrate in which the transparent conductive film was formed in one side is preferable.

As a material which comprises a transparent substrate, glass, resin, etc. are mentioned, for example. As said glass, for example, soda-lime glass, an alkali free glass, etc .; Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, and the like.

Examples of the transparent conductive film include an NESA film (registered trademark of US PPG) made of tin oxide (SnO ₂ ), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), and the like. .

As a method of forming the film of the composition of a 1st composition solution on a board | substrate, it can follow the (i) application method and (ii) dry film method, for example.

(i) When apply | coating method, after apply | coating the solution of a 1st composition on a board | substrate, a film can be formed by heating (prebaking) an application surface.

It does not specifically limit as a coating method of a composition solution, For example, the appropriate method, such as a spraying method, the roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, the inkjet coating method, can be employ | adopted. In particular, a spin coating method or a slit die coating method is preferable.

Although the conditions of prebaking also differ according to the kind, compounding ratio, etc. of each component, Preferably it is about 1 to 15 minutes at 70-120 degreeC.

When the film of the first composition solution is formed on the substrate (ii) When the dry film method is employed, the dry film is a photosensitive layer composed of the photosensitive resin composition of the present invention on a base film, preferably a flexible base film. It is made by laminating (hereinafter referred to as "photosensitive dry film").

The photosensitive dry film may be formed by laminating a photosensitive layer by applying the photosensitive resin composition of the present invention on the base film as a liquid composition, and then removing the solvent. As a photosensitive dry film base film, the film of synthetic resins, such as polyethylene terephthalate (PET), polyethylene, a polypropylene, polycarbonate, polyvinyl chloride, can be used, for example. The thickness of the base film is suitably in the range of 15 to 125 mu m. As for the thickness of the photosensitive layer obtained, about 1-30 micrometers is preferable. Removal of the solvent is preferably carried out by heating at about 80 to 150 ° C. for about 1 to 10 minutes.

In addition, a photosensitive dry film can also be laminated | stacked and preserve | saved further on the photosensitive layer at the time of nonuse. This cover film does not need to be peeled off when not in use, and needs to have appropriate release property so that it can be easily peeled off when used. As a cover film which satisfies these conditions, the film which apply | coated or baked the silicone type mold release agent to the surface of synthetic resin films, such as a PET film, a polypropylene film, a polyethylene film, and a polyvinyl chloride film, can be used, for example. The thickness of the cover film is usually about 25 μm.

When the first composition is used as a solution, its solid content concentration (ratio of the total weight of the composition from which the solvent is removed from the composition) is preferably 5 to 80% by weight. More preferable solid content concentration changes with the formation method of a film. As solid content concentration in the case of employ | adopting (i) coating method for formation of a film, 15-30 weight% is preferable, and 50-70 weight% as solid content concentration in the case of employing (ii) dry film method for formation of a film is desirable.

In addition, the film thickness of the film formed on a board | substrate is although it does not specifically limit, Preferably it is 0.5-10 micrometers, More preferably, it is about 1.0-7.0 micrometers.

(2) exposing radiation to at least a portion of the film

Subsequently, radiation is exposed to at least a portion of the formed film. When exposing to a part of film, it can be followed by the method of exposing through the photomask which has a predetermined pattern, for example.

As radiation used for exposure, visible light, ultraviolet rays, far ultraviolet rays, etc. can be used. As the radiation, radiation having a wavelength in the range of 190 to 450 nm is preferable, and particularly radiation including 365 nm ultraviolet rays is preferable.

The exposure dose is a value measured by an illuminometer (OAI mode 1356, manufactured by OAI Optical Associates Inc.) of the intensity of the exposed radiation at 365 nm, preferably 100 to 10,000 J / m ² , more preferably 1,500 to 3,000 J / m ² .

(3) Process of developing film after exposure

Next, by developing the film after exposure, an unnecessary part is removed and a predetermined pattern is formed.

As a developing solution used for image development, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia; Aliphatic primary amines such as ethylamine and n-propylamine; Aliphatic secondary amines such as diethylamine and di-n-propylamine; Aliphatic tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] Alicyclic tertiary amines such as -5-nonene; Aromatic tertiary amines such as pyridine, collidine, lutidine and quinoline; Alkanolamines such as dimethylethanolamine, methyldiethanolamine and triethanolamine; Aqueous solutions of alkaline compounds, such as quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, can be used.

In an aqueous solution of the alkaline compound, one or more of water-soluble organic solvents such as methanol and ethanol and surfactants may be added in an appropriate amount.

The developing method may be any known developing method such as puddle method, dipping method or shower method, and the developing time is preferably about 10 to 180 seconds at room temperature.

After the development, for example, washing with running water is performed for 30 to 90 seconds, and then a desired pattern is formed by, for example, air drying with compressed air or compressed nitrogen.

(4) The process of heating the film after image development

Subsequently, the obtained pattern (film) is, for example, an appropriate heating device such as a hot plate or an oven at a predetermined temperature, for example, 100 to 160 ° C. for a predetermined time, for example, for 5 to 30 minutes on an hot plate, in an oven. The predetermined spacer can be obtained by heating (postbaking) for 30 to 180 minutes.

In the conventional radiation-sensitive resin composition used to form the spacer, the obtained spacer could not exhibit sufficient performance unless the heat treatment was performed at a temperature of about 180 to 200 ° C. or higher, but the first composition exhibited a lower heating temperature than the conventional one. As a result, it is possible to produce a spacer excellent in various performances such as yellowing and deformation of the resin substrate without compressive strength, rubbing resistance during liquid crystal alignment, adhesion with a transparent substrate, and the like.

<Method of Forming Interlayer Insulating Film or Micro Lens Using Second Composition>

The method of forming an interlayer insulation film or microlens using a 2nd composition is to perform the following process (1)-(4) in the order described below.

(1) forming a film of the second composition on the substrate,

(2) exposing radiation to at least a portion of the film;

(3) developing the film after exposure, and

(4) The process of heating the film after image development.

(1) Process of forming film of 2nd composition on board | substrate

In process (1), a 2nd composition solution is apply | coated to the surface of a board | substrate, and then, prebaking is performed preferably, a solvent is removed and a film of a 2nd composition is formed.

As a kind of substrate which can be used, a glass substrate, a silicon wafer, and the board | substrate with which the various metal was formed in these surfaces are mentioned, for example.

It does not specifically limit as a coating method of a composition solution, For example, the appropriate method, such as a spraying method, the roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, the inkjet coating method, can be employ | adopted. In particular, a spin coating method or a slit die coating method is preferable. The conditions for prebaking vary depending on the type of each component, the use ratio and the like. For example, it can be made into about 30 to 15 minutes at 60-110 degreeC.

As a film thickness of the film formed, it is a value after prebaking, for example, when forming an interlayer insulation film, for example, 3-6 micrometers, and forming a microlens, for example, 0.5-3 micrometers is preferable.

(2) exposing radiation to at least a portion of the film

In the step (2), the formed film is irradiated with radiation through a mask having a predetermined pattern. Thereafter, in the subsequent step (3), the developer is developed using a developing solution, and patterning is performed by removing the irradiated portion of the radiation. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like.

As said ultraviolet-ray, g line | wire (wavelength 436 nm), i line | wire (wavelength 365 nm), etc. are mentioned, for example. As far ultraviolet rays, KrF excimer laser etc. are mentioned, for example. As X-ray, a synchrotron radiation etc. are mentioned, for example. As a charged particle beam, an electron beam etc. are mentioned, for example.

Among these, ultraviolet rays are preferable, and radiation including at least one of g-ray and i-ray is particularly preferable.

As an exposure amount, when forming an interlayer insulation film, it is preferable that it is 50-1,500 J / m <^2> , and when forming a microlens, it is preferable that it is 50-2,000 J / m <^2> .

(3) Process of developing film after exposure

As a developing solution used for the developing process of a process (3), for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, Di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo Alkali (basic compound) aqueous solutions, such as [5.4.0] -7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonane, can be used. Various aqueous organic solvents which melt | dissolve the aqueous solution which added an appropriate amount of water-soluble organic solvents, such as methanol and ethanol, and surfactant in the said aqueous alkali solution, or 2nd composition can be used as a developing solution.

As the developing method, a suitable method such as a puddle method, a dipping method, a rocking dipping method or a shower method can be used. Although developing time changes with composition of a composition, it can be set as 30 to 120 second, for example.

In addition, what is conventionally known as a composition for forming an interlayer insulating film or a microlens has been required to strictly control the development time because peeling occurs in the formed pattern when the development time exceeds about 20 to 25 seconds from the optimum value. In the case of the radiation sensitive resin composition, even if the excess time from the optimum developing time is 30 seconds or more, good pattern formation is possible and there is an advantage in process management.

(4) The process of heating the film after image development

After the step (3) carried out as described above, the patterned film is preferably rinsed by, for example, running water washing, and preferably, the entire surface is irradiated (post-exposure) with radiation by a high pressure mercury lamp or the like. After performing the decomposition | decomposition process of the 1, 2- quinonediazide compound which remains in a film, this film is heat-processed (post-baking process) by heating apparatuses, such as a hotplate and oven. By this treatment, when the cured film is an interlayer insulating film, the film is cured. On the other hand, when the cured film is a microlens, the film having a pattern shape is melted to form a lens shape.

The exposure amount in the post-exposure step is preferably about 2,000 to 5,000 J / m ² . Heating temperature in hardening process is 120-250 degreeC, for example.

The heating time varies depending on the type of heating device, but for example, when the heat treatment is performed on a hot plate, for example, 5 to 30 minutes, and when the heat treatment is performed in an oven, for example, 30 to 90 minutes may be used. Can be. At this time, the step baking method etc. which perform two or more heating processes can also be used.

In this way, a patterned film corresponding to the target interlayer insulating film or microlens can be formed on the surface of the substrate.

<Method of Forming Protective Film Using Third or Fourth Composition>

The method of forming a protective film using a 3rd or 4th composition performs the following process (1) and (2) in the order described below.

(1) forming a film of the third or fourth composition on the substrate, and

(2) The process of heating the said film.

(1) forming a film of the third or fourth composition on the substrate

First, a film is formed by applying a third or fourth composition solution on a substrate and prebaking to remove the solvent.

As a board | substrate which can be used here, what consists of glass, quartz, silicone, a transparent resin, etc. can be used, for example. Examples of the transparent resin include polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, a ring-opening polymer of cyclic olefins, hydrogenated substances thereof and the like.

As the coating method, for example, an appropriate method such as a spraying method, a roll coating method, a rotary coating method, a bar coating method, an ink jet method, or the like can be adopted, and in particular, a spin coater, a spinless (registered trademark) coater, and a slit die coater are used. Application | coating can be used preferably.

Although the conditions of the said prebaking also differ according to the kind, compounding ratio, etc. of each component, Preferably it is about 1 to 15 minutes at 70-90 degreeC.

(2) heating the film

Subsequently, a target protective film can be formed by heat-processing the film formed above. The treatment temperature during the heat treatment is preferably about 150 to 250 ° C, and the treatment time is preferably about 5 to 30 minutes when using a hot plate as the heating device, and about 30 to 90 minutes when using an oven.

In addition, when the 3rd or 4th composition contains a radiation sensitive acid generator, it is preferable to perform radiation irradiation (exposure treatment) before a heating process after prebaking. As the radiation used for this exposure treatment, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like can be employed, but ultraviolet rays containing light having a wavelength of 190 to 450 nm are preferable. The exposure dose is preferably 100 to 20,000 J / m ² , more preferably 150 to 10,000 J / m ² .

The film thickness of the protective film thus formed is preferably 0.1 to 8 µm, more preferably 0.1 to 6 µm, and still more preferably 0.1 to 4 µm. However, when a protective film is formed on the board | substrate which has the level difference of a color filter, the said film thickness means the thickness in the uppermost part of a color filter.

<Method of Forming Protective Film Using Fifth Composition>

The method of forming a protective film using a 5th composition is to perform the following process (1)-(3) in the order described below.

(1) mixing the first liquid and the second liquid of the fifth composition,

(2) forming a film of the mixed liquid on a substrate, and

(3) A step of heating the coating.

(1) Process of mixing the 1st liquid and 2nd liquid of 5th composition

First, the 1st liquid and 2nd liquid of 5th composition are mixed, and the coating composition solution is prepared. The mixing ratio of the first liquid and the second liquid is preferably 20 to 60 parts by weight of the amount of the (F) curing agent included in the second liquid relative to 100 parts by weight of the polymer (A ′) contained in the first liquid, More preferably, it is the ratio used as 20-50 weight part.

After mixing a 1st liquid and a 2nd liquid, and preparing a composition solution, it is preferable to use for the next process (2) within 24 hours.

(2) forming a coating film of the mixed liquid on a substrate

(3) heating the film

Said process (2) and process (3) form "(1) the film of a 3rd or 4th composition on a board | substrate in the above-mentioned" method of forming a protective film using a 3rd or 4th composition ", respectively. Step "and" (2) step of heating said film ".

As is clear from the examples described below, all of the above-described methods are substantially free of sublimation in the heating step (firing step) in the cured film forming step, and can form a cured film under clean conditions, in particular, the second. The composition has a high development margin in the development process. Moreover, the cured film obtained is excellent in pattern shape, compressive strength, and rubbing tolerance in the case of the spacer from a 1st composition. When a cured film is an interlayer insulation film from a 2nd composition, it is high in heat resistance and solvent resistance, low in dielectric constant, and shows high transmittance | permeability. When the cured film is a microlens from the second composition, it exhibits a good melt shape (desirable curvature radius), high heat resistance and solvent resistance, and high transmittance. In the case where the cured film is a protective film from the third to fifth compositions, the heat resistance and the surface hardness are high, and high transparency is excellent, and the ability to flatten the step on the base substrate is excellent.

<< liquid crystal display element >>

When the cured film formed similarly to the above is a spacer or a protective film, these can be used suitably for a liquid crystal display element.

The liquid crystal display element described below is equipped with the spacer or protective film formed similarly to the above.

Such a liquid crystal display element is manufactured by the following method, for example. First, two board | substrates with a protective film and a liquid crystal aligning film are manufactured, and two board | substrates are opposed through a gap (cell gap) so that the liquid crystal aligning direction in each alignment film may be orthogonal or antiparallel, and two board | substrate peripheral parts The liquid crystal is filled in the cell gap partitioned by the spacer, the surface of the board | substrate, and the spacer via a spacer, and the filling hole is sealed and a liquid crystal cell is comprised. Further, the liquid crystal display element is bonded to the outer surface of the liquid crystal cell, that is, the other surface side of each substrate constituting the liquid crystal cell by bonding the polarizing plate so that its polarization direction is coincident with or perpendicular to the liquid crystal alignment direction of the protective film formed on one surface of the substrate. You can get it.

As said liquid crystal, a nematic liquid crystal and a smectic liquid crystal are mentioned, for example. Especially, a nematic type liquid crystal is preferable, for example, a Schiff base type liquid crystal, a subfamily clock liquid crystal, a biphenyl type liquid crystal, a phenyl cyclohexane type liquid crystal, an ester type liquid crystal, a terphenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal, a pyrimi Din type liquid crystals, dioxane type liquid crystals, bicyclooctane type liquid crystals, cuban type liquid crystals, etc. are used. In addition, these liquid crystals are, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonate, cholesteryl carbonate, and trade names "C-15" and "CB-15" (manufactured by Merck). The chiral agent etc. which are sold can also be added and used. Ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

As a polarizing plate used on the outer side of a liquid crystal cell, the polarizing plate etc. which made the polarizing film called H film | membrane which absorbed iodine while extending | stretching orientation of polyvinyl alcohol by the cellulose acetate protective film, or the polarizing plate which consists of H film itself are mentioned.

<Example>

Although a synthesis example and an Example are shown to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example.

Gel permeation chromatography was measured on the polymer synthesize | combined in the synthesis example of the following polymer on the following conditions, the weight average molecular weight (Mw) and number average molecular weight (Mn) of polystyrene conversion are calculated | required, and molecular weight distribution (Mw / Mn) is calculated | required. Calculated.

Apparatus: GPC-l01 (manufactured by Showa Denko Co., Ltd.)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804

Mobile phase: tetrahydrofuran containing 0.5 wt% phosphoric acid

(I) Preparation and Evaluation of the First Composition

Polymer Synthesis Example

Synthesis Example  One

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 5 parts by weight of tetraethylthiuram disulfide as a molecular weight control agent, and diethylene glycol diethyl ether in a flask equipped with a cooling tube and a stirrer. 200 parts by weight of styrene, 20 parts by weight of styrene, 17 parts by weight of methacrylic acid, 18 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate and 45 parts by weight of glycidyl methacrylate And nitrogen-substituted, the reaction solution was heated to 70 ° C while gradually stirring, and maintained at this temperature to polymerize for 4 hours. Then, 3 weight part of 2,2'- azobis (2, 4- dimethylvaleronitrile) was added, and superposition | polymerization was continued for 3 hours and the solution containing a copolymer was obtained. This resin was Mw = 12,000 and Mw / Mn = 1.60. This resin is called "resin (A-1)."

Synthesis Example  2

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 5 parts by weight of tetraethylthiuram disulfide as a molecular weight control agent, and diethylene glycol diethyl ether in a flask equipped with a cooling tube and a stirrer. 200 parts by weight of styrene, 5 parts by weight of styrene, 16 parts by weight of methacrylic acid, 34 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, 35 parts by weight of glycidyl methacrylate 5 parts by weight of methylglycidyl methacrylate was added thereto, followed by nitrogen substitution, and stirring was started slowly. After raising the temperature of the solution to 70 DEG C and maintaining this temperature for 8 hours, 3 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, followed by further stirring at 70 DEG C for 4 hours. , 200 parts by weight of diethylene glycol ethylmethyl ether was added to obtain a solution containing a copolymer (A-2). Mw of the obtained copolymer (A-2) was 12,000 and molecular weight distribution (Mw / Mn) was 1.40.

compare Synthesis Example  One

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer, followed by 20 parts by weight of styrene and methacryl 17 parts by weight of acid, 18 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, and 45 parts by weight of glycidyl methacrylate were substituted for nitrogen, followed by temperature stirring. Was heated to 70 deg. C and maintained at this temperature for 4 hours to obtain a solution containing a copolymer. Solid content concentration of this solution was 29.5 weight%, Mw of the obtained copolymer was 13,000, molecular weight distribution (Mw / Mn) was 2.4, and residual monomer was 7%. This copolymer is called "copolymer (a-1").

Example  One

Radiation  Preparation of Resin Composition

A solution containing the polymer (A-1) synthesized in Synthesis Example as component (A) in an amount corresponding to 100 parts by weight (solid content) of polymer (A-1), and dipentaerythritol hexaacrylic as (B) component 8 parts by weight of 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole as 100 parts by weight and (C) component and γ-gly as an adhesion aid 5 parts by weight of cydoxypropyltrimethoxysilane, 0.5 parts by weight of FTX-218 (trade name, manufactured by Neos) as a surfactant, and 0.5 parts by weight of 4-methoxyphenol as a storage stabilizer were mixed, and the solid content concentration of the composition was 20 After dissolving by adding propylene glycol monomethyl ether acetate to a weight%, the composition solution was prepared by filtration with a Millipore filter having a pore size of 0.5 mu m.

Evaluation of the composition solution manufactured similarly to the above was performed as follows.

Spacer  formation

After apply | coating the said composition solution using a spinner on the alkali free glass substrate, it prebaked for 3 minutes on the 90 degreeC hotplate, and formed the film of 6.0 micrometers in film thicknesses.

Subsequently, the obtained film was irradiated with ultraviolet light having an intensity of 250 W / m ² at 365 nm for 10 seconds through a photomask having a residual pattern of 10 μm each side. Thereafter, the solution was developed at 25 ° C. for 60 seconds with a 0.05% by weight aqueous solution of potassium hydroxide, and then washed with pure water for 1 minute. In addition, the spacer which has a predetermined | prescribed pattern was formed by post-baking at 150 degreeC for 120 minutes in oven.

Evaluation of the resolution

When the pattern was formed in the above-mentioned "formation of spacer", the case where the residual pattern was resolved was evaluated as good (○) and the case where it was not resolved as defective (x). The resolution of the composition prepared above was good.

Evaluation of sensitivity

The residual film rate (film thickness after development / initial film thickness x 100 (%) after development) of the pattern obtained by said "formation of spacer" was computed. As a result of evaluating the case where this value is 90% or more as good ((circle)) and the case where it is less than 90% as bad (x), the sensitivity of the composition produced above was favorable.

Evaluation of pattern shape

The cross-sectional shape of the pattern obtained by said "formation of spacer" was observed with the scanning electron microscope, and it evaluated by which of A-D shown in FIG. At this time, when the pattern edge is a forward taper shape or a vertical shape like A or B, it can be said that the pattern shape as a spacer is favorable. On the other hand, as shown in C, when the sensitivity is insufficient, the residual film ratio is low, the cross-sectional area is small compared to A or B, and the bottom surface of the cross-sectional shape is a flat convex lens shape, the pattern shape as a spacer is poor, and As shown, even when the cross-sectional shape was an inverted taper shape, the pattern shape as a spacer was regarded as defective because there was a high possibility that the pattern would peel off during the subsequent rubbing treatment.

The cross-sectional shape of the spacer formed from the composition produced above was B, and the cross-sectional shape was favorable.

Evaluation of compressive strength

When a load of 10 mN was applied to a pattern obtained in the above-described "Formation of spacer" by a planar indenter having a diameter of 50 µm using a micro compression tester (manufactured by Shimadzu Corporation, model "MCTM-200"). The deformation amount was measured at a measurement temperature of 23 ° C. When this value is 0.5 micrometer or less, it can be said that compressive strength is favorable.

The deformation amount of the spacer formed from the composition prepared above was 0.41 mu m, and the compressive strength was good.

Loving  Assessment of tolerance

After apply | coating a liquid crystal aligning agent (JSR Corporation make, brand name "AL3046") to the board | substrate with which the pattern was formed like the said "formation of spacer" using the printing machine for liquid crystal aligning film coating, it heats at 180 degreeC for 1 hour, After the heating, a coating film of an alignment agent having a thickness of 0.05 μm was formed. Then, the rubbing process was performed on the coating film on the conditions of the rotation speed of a roll of 500 rpm, and the moving speed of 1 cm / sec of the stage using the rubbing machine which has the roll wound up the polyamide cloth. At this time, the presence or absence of cutting or peeling of the pattern was examined.

No cutting or peeling of the pattern was observed for the substrate having the pattern formed from the composition prepared above.

Evaluation of adhesion

Except not using the mask of a residual pattern, it carried out similarly to said "formation of a spacer," and formed the cured film. The adhesiveness of the cured film formed here was evaluated by the 8.5.2 checker eye tape method in the adhesion test of JISK-5400 (1900) 8.5. The remaining number of checkerboard eyes was 100.

Sublimation  evaluation

The composition solution was applied onto a silicon substrate using a spinner, and then prebaked at 90 ° C. on a hot plate for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was exposed using a Canon Inc. exposure machine (type "PLA-501F", ultra-high pressure mercury lamp) so as to have an integrated irradiation amount of 3,000 J / m ² , and the substrate after exposure was exposed at 1 to 220 ° C in a clean oven. It heated for time and obtained the cured film. The bare silicon wafer for cooling was attached to the upper side of the obtained cured film by 1 centimeter space | interval, and 230 degreeC and the heat processing for 1 hour were performed on the hotplate. After continuously processing 20 sheets of the silicon substrate in which the cured film was formed separately in the same manner as described above without replacing the cooling bare silicon wafer, and visually observing the presence or absence of the sublimation adhered to the bare silicon, Not confirmed.

Evaluation of Voltage Retention

The radiation-sensitive resin composition prepared above using a spinner was formed on a soda glass substrate on which a SiO ₂ film was formed to prevent elution of sodium ions, and an ITO (indium-tin oxide alloy) electrode was deposited in a predetermined shape. It applied and prebaked for 10 minutes in 90 degreeC clean oven, and formed the coating film of 2.0 micrometers in thickness. Subsequently, a high pressure mercury lamp was used to expose the radiation containing the wavelengths of 365 nm, 405 nm and 436 nm to the coating film at an exposure amount of 2,000 J / m ² without interposing a photomask. Furthermore, it post-baked at 230 degreeC for 30 minutes, hardened the coating film, and formed the cured film.

Subsequently, the substrate having this cured film and the soda glass substrate which just deposited the ITO electrode to a predetermined shape on the surface are opposed to each other, and the four sides are bonded together using a sealing agent mixed with 0.8 mm glass beads, leaving a liquid crystal injection hole. After inject | pouring the liquid crystal MLC6608 (brand name) by a Merck company, the liquid crystal cell was produced by sealing a liquid crystal injection port.

The liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the applied voltage was 5.5 V square wave, and the measurement frequency was 60 Hz by the Toyo Technica Co., Ltd. liquid crystal voltage retention measuring system VHR-1A type (brand name). As a result of measuring the voltage retention, the voltage retention was 97%. In addition, a voltage retention is a value represented by following formula (1) here.

Voltage retention (%) = (liquid crystal cell potential difference after 16.7 milliseconds) / (voltage applied at 0 milliseconds) × 100

When the voltage retention of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot keep the applied voltage at a predetermined level for a time of 16.7 milliseconds and cannot align the liquid crystal sufficiently, and such a liquid crystal cell is referred to as "splitting". High risk of causing.

Example  2 to 10 and Comparative example  One

In the "production of a radiation sensitive resin composition" of Example 1, the composition was prepared in the same manner as in Example 1 except that the types and amounts shown in Table 1 were used as the components (A), (B) and (C), respectively. Was prepared and evaluated. The evaluation results are shown in Table 2.

In addition, abbreviated-name which shows each component in Table 1 respectively means the following. In addition, when the kind and quantity of a component are couple | bonded with "/", it shows what used multiple types together as the component by the quantity described in the table, respectively. In addition, "-" in a table | surface shows that the component corresponded to the column was not used.

(B) component

B-1: dipentaerythritol hexaacrylate

(C) component

C-1: 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole

C-2: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole

C-3: 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone

C-4: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1

Radiation-sensitizer

H-1: 4,4'-bis (dimethylamino) benzophenone

H-2: 2-mercaptobenzothiazole

H-3: pentaerythritol tetra (mercaptoacetate)

(II) Preparation and Evaluation of the Second Composition

Polymer Synthesis Example

Synthesis Example  3

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 5 parts by weight of tetraethylthiuram disulfide as a molecular weight control agent, and diethylene glycol diethyl ether in a flask equipped with a cooling tube and a stirrer. 200 parts by weight of styrene, 20 parts by weight of styrene, 20 parts by weight of methacrylic acid, 20 parts by weight of tricyclo [5,2.1.0 ^2,6 ] decane-8-ylmethacrylate and 40 parts by weight of glycidyl methacrylate After the addition, nitrogen replacement was carried out, and the reaction solution was heated to 70 ° C. while gradually stirring to maintain this temperature and polymerized for 6 hours. Then, 3 weight part of 2,2'- azobis (2, 4- dimethylvaleronitrile) was added, and superposition | polymerization was continued for 3 hours and the solution containing copolymer (A-3) was obtained. Polymer (A-3) had Mw = 11,000 and Mw / Mn = 1.60.

Synthesis Example  4

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 5 parts by weight of tetraethylthiuram disulfide as a molecular weight control agent, and diethylene glycol diethyl ether in a flask equipped with a cooling tube and a stirrer. 200 parts by weight of N-cyclohexylmaleimide, 10 parts by weight of styrene, 10 parts by weight of methacrylate, 20 parts by weight of methacrylic acid, 20 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate And 40 parts by weight of glycidyl methacrylate were substituted for nitrogen, and then the reaction solution was heated to 70 ° C while gradually stirring, and maintained at this temperature to polymerize for 6 hours. Then, the solution containing copolymer (A-4) was obtained by adding 3 weight part of 2,2'- azobis (2, 4- dimethylvaleronitrile), and continuing superposition | polymerization for 3 hours. Copolymer (A-4) had Mw = 12,000 and Mw / Mn = 1.70.

Synthesis Example  5

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 5 parts by weight of tetraethylthiuram disulfide (molecular weight control agent) and diethylene glycol dimethyl ether in a flask equipped with a cooling tube and a stirrer 200 parts by weight of styrene, 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 20 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, 40 parts by weight of glycidyl methacrylate And 10 parts by weight of p-vinylbenzyl glycidyl ether were substituted for nitrogen, and then the reaction solution was heated to 70 ° C. while gradually stirring to maintain this temperature and polymerized for 6 hours. Then, 4 weight part of 2,2'- azobis (2, 4- dimethylvaleronitrile) was added, and superposition | polymerization was continued for 3 hours and the solution containing copolymer (A-5) was obtained. Copolymer (A-5) had Mw = 13,000 and Mw / Mn = 1.50.

compare Synthesis Example  2

8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 20 parts by weight of styrene, 20 parts by weight of methacrylic acid, tricyclo [5.2.1.0 ^{2, 6} ] 20 parts by weight of decane-8-yl methacrylate, 40 parts by weight of glycidyl methacrylate and 200 parts by weight of diethylene glycol diethyl ether were substituted with nitrogen, and then stirring was gradually started. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 6 hours to obtain a polymer solution containing the copolymer (a-2).

The polystyrene reduced weight average molecular weight (Mw) of the copolymer (a-2) was 9,500 and molecular weight distribution (Mw / Mn) was 2.4.

Example 11

Radiation  Preparation of Resin Composition

The solution containing the polymer (A-3) is equivalent to 100 parts by weight of solids of the polymer (A-3), and 4,4 '-[1- [4- [1- [4- as a component (D) 30 parts by weight of a condensate of hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol) was mixed to obtain a solid content concentration. After dissolving in diethylene glycol ethyl methyl ether so that it may be 30 weight%, the solution of the radiation sensitive resin composition was prepared by excess with the membrane filter of diameter 0.2micrometer.

Performance evaluation as an interlayer insulating film

The various characteristics as an interlayer insulation film were evaluated as follows using the radiation sensitive resin composition manufactured as mentioned above.

Evaluation of sensitivity

The above-mentioned radiation sensitive resin composition was apply | coated on the silicon substrate using the spinner, and it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in thickness. After exposure by changing exposure time with Canon Co., Ltd. product, PLA-501F exposure machine (ultra-high pressure mercury lamp) through the pattern mask which has a predetermined | prescribed pattern to the obtained coating film, it is exposed to tetramethylammonium hydroxide aqueous solution of 0.4 weight% of concentration. It developed by the puddle method at 25 degreeC for 90 second. Flowing water was washed for 1 minute with ultrapure water and dried to form a pattern on the silicon substrate. At this time, the exposure amount required in order to completely dissolve the space pattern of the line-and-space (10: 1) of 3.0 micrometers was investigated. As a result of evaluating this value as a sensitivity, it was 550 J / m <^2> . When this value is 1,000 J / m <^2> or less, it can be said that a sensitivity is favorable.

Evaluation of developing margin

The above-mentioned radiation sensitive resin composition was apply | coated on the silicon substrate using the spinner, and it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in thickness. The obtained coating film was measured by the said "evaluation of sensitivity" using Canon Inc. make, PLA-501F exposure machine (ultra-high pressure mercury lamp) through the mask which has a pattern of a line and space (10 to 1) of 3.0 micrometers. The exposure was performed at an exposure amount corresponding to the value of sensitivity. Thereafter, using a tetramethylammonium hydroxide aqueous solution having a concentration of 0.4% by weight, development was carried out by a puddle method at 25 ° C with a variable development time. Subsequently, flowing water was washed for 1 minute with ultrapure water, and dried to form a pattern on the wafer. At this time, it was 60 second as a result of investigating developing time required for line line width to be 3 micrometers as an optimal developing time. Moreover, when developing was further continued from this optimum developing time, it was 30 second when the time until the 3.0 micrometer line / pattern peeled was measured as a developing margin. When this value is 30 seconds or more, the development margin can be said to be good.

Solvent-resistant  evaluation

The above-mentioned radiation sensitive resin composition was apply | coated on the silicon substrate using the spinner, and it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in thickness. The obtained coating film was exposed so that the integrated irradiation amount might be 3,000 J / m ² using an Canon exposure machine (type "PLA-5O1F" (ultra high pressure mercury lamp)). The silicon substrate after exposure was heated in 220 degreeC for 1 hour in the clean oven, and the cured film was obtained. It was 2.3 micrometers when the film thickness (T1) of the obtained cured film was measured. The silicon substrate on which this cured film was formed was immersed in dimethyl sulfoxide for 20 minutes in temperature control, and the film thickness t1 of the cured film was measured, and the film thickness change rate by immersion {| t1-T1 | / T1} It was 0.1% as a result of calculating x100 (%). When this value is 5% or less, it can be said that solvent resistance is favorable.

In addition, since the patterning of the film formed is unnecessary in evaluation of solvent resistance, the irradiation process and the image development process were abbreviate | omitted, and only the coating film formation process, the postbaking process, and the heating process were used for evaluation.

Evaluation of heat resistance

It was 2.3 micrometers when the film thickness (T2) of the cured film obtained by forming a cured film similarly to the evaluation of the said solvent resistance was measured. Subsequently, after further baking this board | substrate with a cured film at 240 degreeC in clean oven for 1 hour, the film thickness t2 of the said cured film was measured, and the film thickness change rate by further baking {| t2-T2 | / T2 } X 100 (%) was calculated, and the result was 0%. When this value is 5% or less, it can be said that solvent resistance is favorable.

Evaluation of transparency

The evaluation of the said solvent resistance was performed similarly except having used the glass substrate "Corning 7059" (made by Corning Corporation) instead of the silicon substrate, and the cured film was formed on the glass substrate. The light transmittance of the glass substrate having this cured film was loaded with a Corning 7059 having no film in the reference cell using a spectrophotometer "150-20 type double beam (manufactured by Hitachi Seisakusho Co., Ltd.), 400-800 nm. Measured in the wavelength range. It was 92% when the value of the minimum light transmittance at this time was examined. When this value is 90% or more, it can be said that transparency is favorable.

Relative dielectric constant  evaluation

The radiation sensitive resin composition prepared above was apply | coated using the spinner on the polished SUS304 board | substrate, and it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in film thicknesses. The obtained coating film was exposed to a cumulative irradiation amount of 3,000 J / m ² using an Canon exposure machine, model "PLA-501F" (ultra-high pressure mercury lamp), and the substrate was cured by heating at 220 캜 for 1 hour in a clean oven. A membrane was obtained.

The Pt / Pd electrode pattern was formed on this cured film by the vapor deposition method, and the sample for dielectric constant measurement was manufactured. The relative dielectric constant of the substrate was measured at a frequency of 10 kHz using a CV method using a Yokogawa Hewlett-Packard Co., Ltd. product, an HP16451B electrode, and an HP4284A Precision LCR meter, and the relative dielectric constant was 3.3. When this value is 3.6 or less, it can be said that the dielectric constant is good.

In addition, since the patterning of the film formed is unnecessary in the evaluation of the dielectric constant, only the coating film formation process, the postbaking process, and the heating process were used for evaluation, omitting the irradiation process and the development process.

Sublimation  evaluation

As a result of evaluating similarly to Example 1 using the radiation sensitive resin composition manufactured above, a sublimation was not confirmed.

Evaluation of Voltage Retention

As a result of evaluation in the same manner as in Example 1 using the radiation-sensitive resin composition prepared above, the voltage retention was 97%.

Example  12 to 15 and Comparative example  2

In Example 11, the radiation sensitive resin composition was produced and evaluated similarly to Example 11 except having used the kind and quantity as described in Table 3 as (A) component and (D) component. The evaluation results are shown in Table 4.

In addition, in Example 15, when forming a coating film on the board | substrate, the coating method using a slit die coater was used instead of the spin coating method.

In Table 3, the abbreviation of a component means the following, respectively.

(D) component

(D-1): 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphtho Condensate of quinonediazide-5-sulfonic acid chloride (2.0 moles)

(D-2): 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphtho Condensate of quinonediazide-5-sulfonic acid chloride (1.0 mole)

(D-3): 2,3,4,4'-tetrahydroxybenzophenone- (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid ester (2.44 mol)

(D-4): 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphtho Condensate of quinonediazide-4-sulfonic acid chloride (2.0 mol)

Example  16

Radiation  Preparation of Resin Composition

The solution containing the polymer (A-3) is equivalent to 100 parts by weight of solids of the polymer (A-3), and 4,4 '-[1- [4- [1- [4- as a component (D) 20 parts by weight of a condensate of hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol) was mixed to obtain a solid content concentration. The solution was dissolved in diethylene glycol ethylmethyl ether so as to be 30% by weight, and then filtered through a membrane filter having a diameter of 0.2 µm to prepare a solution of radiation-sensitive resin composition.

Performance Evaluation as a Micro Lens

The various characteristics as a microlens were evaluated as follows using the radiation sensitive resin composition manufactured as mentioned above.

Evaluation of sensitivity

The above-mentioned radiation sensitive resin composition was apply | coated on the silicon substrate using the spinner, and it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in thickness. The exposure time was changed and exposed by the Nikon Corporation make, NSR1755i7A reduction projection exposure machine (NA = 0.50, (lambda == 365 nm) through the pattern mask which has a predetermined | prescribed pattern to the obtained coating film, and tetramethylammonium hydroxide of 0.4 weight% of concentration. It developed by the puddle method at 25 degreeC as aqueous solution of rock seed for 1 minute. Rinse with water and dry to form a pattern on the silicon substrate. At this time, it was 600 J / m <^{2> when the} exposure amount required for the space line width of a 0.8 micrometer line and space pattern (1 to 1) to be 0.8 micrometer was investigated as a sensitivity.

Evaluation of developing margin

The above-mentioned radiation sensitive resin composition was apply | coated on the silicon substrate using the spinner, and it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in thickness. The exposure amount corresponding to the value of the sensitivity measured by the said "evaluation of sensitivity" with the Nikon Corporation make, NSR1755i7A reduction projection exposure machine (NA = 0.50, (lambda == 365 nm) through the pattern mask which has a predetermined | prescribed pattern in the obtained coating film It exposed and it developed by the puddle method at 25 degreeC using the tetramethylammonium hydroxide aqueous solution of 0.4 weight% of concentration as a variable. Rinse with water and dry to form a pattern on the silicon substrate. It was 60 second when the developing time required for the space line width of a 0.8 micrometer line and space pattern (1 to 1) to be 0.8 micrometer was made into the optimal developing time. In the case where further development was continued from the optimum development time, the time until the pattern having a width of 0.8 µm was peeled off was measured as the development margin, and found to be 30 seconds. When this value is 30 seconds or more, the development margin can be said to be good.

Solvent-resistant  evaluation

The above-mentioned radiation sensitive resin composition was apply | coated on the silicon substrate using the spinner, and it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in thickness. The obtained coating film was exposed using Canon's exposure machine and model "PLA-5O1F" (ultra-high pressure mercury lamp) so that the integrated irradiation amount was 3,000 J / m ² , and the silicon substrate was heated at 220 ° C. for 1 hour in a clean oven. To obtain a cured film. It was 2.3 micrometers when the film thickness (T3) of the cured film obtained here was measured. After immersing the silicon substrate having this cured film in isopropyl alcohol temperature controlled at 50 ° C. for 10 minutes, the film thickness t3 of the cured film was measured, and the film thickness change rate by immersion {| t3-T3 | / T3} It was 0.1% as a result of calculating x100 (%). When this value is 5% or less, it can be said that solvent resistance is favorable.

In addition, since the patterning of the film formed is unnecessary in evaluation of solvent resistance, the irradiation process and the image development process were abbreviate | omitted, and only the coating film formation process, the postbaking process, and the heating process were used for evaluation.

Formation of microlenses (evaluation of microlens shape)

The above-mentioned radiation sensitive resin composition was apply | coated on the silicon substrate using the spinner, and it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 3.0 micrometers in thickness. The value of the sensitivity measured by said "evaluation of sensitivity" with the Nikon Corporation make, NSR1755i7A reduction projection exposure machine (NA = 0.50, (lambda == 365 nm) through the pattern mask which has a 4.0 micrometer dot and a 2.0 micrometer space pattern on the obtained coating film. It exposed at the exposure amount equivalent to, and developed by the puddle method at 25 degreeC for 1 minute as tetramethylammonium hydroxide aqueous solution of 0.4 weight% of concentration. Rinsed with water and dried to form a pattern on a silicon substrate. Subsequently, after exposing so that accumulated irradiation amount might be 3,000 J / m <^2> by the Canon Inc. exposure machine and model "PLA-501F" (ultra high pressure mercury lamp), it heats at 160 degreeC for 10 minutes with a hotplate, and 230 degreeC The pattern was melted by further heating for 10 minutes at to form a microlens.

As a result of measuring the dimension (diameter) of the bottom portion (surface in contact with the substrate) of the formed microlens, the cross-sectional shape was a semi-convex lens shape as shown in Fig. 2A. When the dimension of the microlens bottom portion is more than 4.0 µm and less than 5.0 µm, and the cross-sectional shape of the microlens is a semi-convex lens shape as shown in Fig. 2A, the microlens shape can be said to be good. If the diameter of the microlens bottom is 5.0 µm or more, the adjacent lenses are in contact with each other, which is not preferable. Moreover, when the cross-sectional shape of a microlens is substantially trapezoidal shape like FIG.2 (b), it is a shape defect.

Evaluation of heat resistance, evaluation of transparency and Sublimation  evaluation

These evaluations were performed in the same manner as the respective evaluations in the performance evaluation as the interlayer insulating film. The film thickness after curing in heat resistance evaluation was 2.3 µm, the film thickness change rate was 0%, the minimum light transmittance in the range of 400 to 800 nm in the transparency evaluation was 92%, and the bare silicon surface for cooling in the sublimation evaluation was evaluated. No sublimates were observed.

Example  17 to 20 and Comparative example  3

In Example 16, the radiation sensitive resin composition was produced and evaluated similarly to Example 16 except having used the kind and quantity as shown in Table 5 as (A) component and (D) component, respectively. The evaluation results are shown in Table 6.

In addition, abbreviated-name of (D) component column in Table 5 is the same as that of Table 3.

(III) Preparation and Evaluation of the Fifth Composition

Polymer Synthesis Example

Synthesis Example  6

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 5 parts by weight of tetraethylthiuram disulfide (molecular weight control agent) and diethylene glycol diethyl in a flask equipped with a cooling tube and a stirrer 200 parts by weight of ether was added, and then 80 parts by weight of glycidyl methacrylate and 20 parts by weight of styrene were added thereto, followed by nitrogen substitution, and the reaction solution was heated to 70 deg. C while stirring gradually, and maintained at this temperature for polymerization for 6 hours. Then, 3 weight part of 2,2'- azobis (2, 4- dimethylvaleronitrile) was added, and superposition | polymerization was continued for 3 hours and the solution containing polymer (A-6) was obtained. This polymer (A-6) was Mw = 12,000 and Mw / Mn = 1.60.

compare Synthesis Example  3

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methylethyl ether were added, followed by 50 parts by weight of styrene and methacryl. 50 parts by weight of acid glycidyl was added thereto, nitrogen was substituted, and the mixture was slowly stirred to raise the temperature of the reaction solution to 70 ° C. and maintained at this temperature for polymerization for 5 hours to obtain a solution containing the polymer (a-3). The polystyrene reduced weight average molecular weight (Mw) of the polymer (a-3) was 14,000, and molecular weight distribution (Mw / Mn) was 1.8.

Example  21

Two-component  Preparation of Curable Resin Composition

<Production of First Liquid>

Bisphenol A novolac as an amount corresponding to 100 parts by weight of the solid content of the copolymer (A-6) and the solution containing the copolymer (A-6) obtained in Synthesis Example 6 as the component (A '). 10 parts by weight of the type epoxy resin `` Epicoat 157S65 '' (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), 15 parts by weight of γ-glycidoxypropyltrimethoxysilane as an adhesion aid, and SH-28PA (Toray Dow as a surfactant). 0.1 parts by weight of Corning Silicone Co., Ltd. were mixed, and propylene glycol monomethyl ether acetate was added so that the solid content concentration in the first liquid was 20% by weight, followed by filtration with a Millipore filter having a pore diameter of 0.5 µm. A liquid was prepared.

<Production of Second Liquid>

As the component (F), 35 parts by weight of trimellitic anhydride was dissolved in 65 parts by weight of diethylene glycol methylethyl ether to prepare a second liquid.

<Production of Curable Resin Composition>

The first solution and the second solution were mixed to prepare a composition solution. This composition solution was colorless and transparent.

Evaluation of Curable Resin Composition

The obtained composition solution was evaluated by forming a protective film on the substrate as described below.

Formation of protective film

After applying the composition solution prepared above using a spinner on a SiO ₂ immersed glass substrate, a pre-baked film was formed by prebaking at 80 ° C. for 5 minutes on a hot plate, and further subjected to heat treatment at 230 ° C. for 60 minutes in an oven. A protective film with a thickness of 2.0 mu m was formed on the film.

Evaluation of protective film

Evaluation of Transparency:

A SiO ₂ immersion glass substrate having no protective film was loaded on a reference cell using a spectrophotometer 150-20 type double beam (manufactured by Hitachi Seisakusho Co., Ltd.) on a SiO ₂ immersion glass substrate having a protective film formed thereon. It was 99% when the transmittance | permeability (%) in 400-800 nm was measured and the minimum value evaluated as transparency. When this value is 95% or more, it can be said that transparency of a protective film is favorable.

Evaluation of heat resistant dimensional stability:

Results for 1 hour heating at 250 ℃ in an oven with respect to the SiO ₂ immersing a glass substrate to form a protective film, and to measure the film thickness before and after heating evaluate the value calculated by equation (2) as a heat-resistant dimensional stability, 99% was . When this value is 95% or more, it can be said that heat-resistant dimensional stability is favorable.

Heat-resistant dimensional stability (%) = (film thickness after heating) / (film thickness before heating) * 100

Evaluation of heat discoloration resistance:

The SiO ₂ immersed glass substrate on which the protective film was formed was heated in an oven at 250 ° C. for 1 hour, and the transmittance was measured in the wavelength range of 400 to 800 nm before and after heating, and was calculated by the following equation (3) using the respective minimum values. It was 3% when the value was evaluated as heat discoloration resistance. When this value is 5% or less, it can be said that heat discoloration resistance is favorable.

Heat discoloration resistance (%) = (minimum value of transmittance before heating)-(minimum value of transmittance after heating)

Evaluation of Surface Hardness:

The hardness was 6H as a result of evaluating the SiO ₂ immersion glass substrate which provided the protective film by the test of 8.4.1 pencil of JISK-5400-1990. When this evaluation result is 4H or harder, it can be said that surface hardness is favorable.

Evaluation of Dynamic Microhardness:

0.1 gf load by the indentation test of a ridge angle 115 ° triangular indenter (Herkovitch type) using a Shimadzu dynamic micro hardness tester DUH-201 (manufactured by Shimadzu Corporation) for the SiO ₂ immersion glass substrate on which the protective film was formed. When the temperature was evaluated as 23 degreeC and 140 degreeC on conditions of the speed of 0.0145 gf / sec and holding time of 5 second, it was 29 at 23 degreeC and was 25 at 140 degreeC.

Evaluation of adhesion:

After performing a pressure cooker test (temperature 120, humidity 100%, measured 24 hours) with respect to the SiO ₂ glass substrate is immersed to form a protective film, SiO ₂ by a snow board 8.5.3 adhesion tape method of JIS K-5400-1990 As a result of evaluating the adhesiveness to the immersion glass substrate, all 100 of the checkerboard eyes remained.

In addition, except that a Cr substrate was used in place of the SiO ₂ immersion glass substrate, a protective film having a thickness of 2.0 µm was formed in the same manner as in the above "formation of the protective film", and the adhesion to the Cr substrate was evaluated in the same manner as described above. All 100 of the checkerboard eyes remained.

Evaluation of leveling power

Pigment-based color resists (trade names "JCR RED 689", "JCR GREEN 706" and "CR 8200B"; above, manufactured by JSR Co., Ltd.) were coated on a SiO ₂ immersion glass substrate with a spinner, respectively, on a hot plate. It prebaked at 150 degreeC for 150 second, and formed the coating film. Subsequently, g / h / i rays (intensity ratios of wavelengths 436 nm, 405 nm and 365 nm = 2.7: 2.5: 4.8) were obtained through a predetermined pattern mask using an exposure machine Canon PLA501F (manufactured by Canon Corporation). After exposure at an exposure dose of 2,000 J / m ² in terms of linear conversion, it was developed using 0.05% potassium hydroxide aqueous solution, washed with ultrapure water for 60 seconds, and further heated at 230 ° C. for 30 minutes in an oven to give red, green, and blue colors 3 A stripe-like color filter (stripe width 100 mu m) of color was formed.

Subsequently, the surface unevenness of the substrate on which this color filter was formed was measured using a surface roughness α-step (manufactured by KLA Tencol Co., Ltd.), and the measurement length was 2,000 μm, the measurement range was 2,000 μm, and the measurement direction was red, green, and blue. Stripe line short axis direction and two directions of stripe line major axis directions of the same color of red, red, green, green, blue, and blue, with measurement score n = 5 (n number of totals = 10) for each direction. It was 1.0 micrometer as a result of measuring the average value of the height difference (nm) of the highest part and the lowest part for every measurement.

Furthermore, after apply | coating the composition solution manufactured by said "production of a radiation sensitive resin composition" using the spinner on the board | substrate with which the color filter was formed in the same way to the above, prebaking for 5 minutes at 80 degreeC on a hotplate The coating film was formed and heat-processed further at 230 degreeC for 60 minute (s) in oven, and the protective film whose film thickness from the upper surface of a color filter is 2.0 micrometers was formed on the color filter.

Subsequently, the unevenness | corrugation of the protective film surface was made to the board | substrate which has a protective film on this color filter similar to the above, and the average value of the height difference (nm) of the highest part and the lowest part was measured, and it was 200 nm. When this value is 300 nm or less, it can be said that planarization ability is favorable.

Evaluation of Sublimation

The composition solution was applied onto a silicon substrate using a spinner, and then prebaked at 90 ° C. on a hot plate for 2 minutes to form a coating film having a thickness of 3.0 μm. This silicon substrate was heated in 220 degreeC in clean oven for 1 hour, and the cured film was obtained. The bare silicon wafer for cooling was attached to the upper side of the obtained cured film by 1 centimeter space | interval, and the heating process was performed at 230 degreeC on the hotplate for 1 hour. After continuously processing 20 sheets of the silicon substrate in which the cured film was formed separately without replacing the cooling bare silicon wafer, the presence or absence of a sublimation adhered to the bare silicon was visually observed, and the sublimation was not confirmed.

Evaluation of Voltage Retention

The radiation-sensitive resin composition prepared above using a spinner was formed on a soda glass substrate on which a SiO ₂ film was formed on the surface to prevent elution of sodium ions, and an ITO (indium-tin oxide alloy) electrode was deposited in a predetermined shape. It applied and prebaked for 10 minutes in 90 degreeC clean oven, and formed the coating film of 2.0 micrometers in thickness. Furthermore, it post-baked at 230 degreeC for 30 minutes, and formed the cured film.

Subsequently, the substrate having this cured film and the soda glass substrate which just deposited the ITO electrode to a predetermined shape on the surface are opposed to each other, and the four sides are bonded together using a sealing agent mixed with 0.8 mm glass beads, leaving a liquid crystal injection hole. After inject | pouring the liquid crystal MLC6608 (brand name) by a Merck company, the liquid crystal cell was produced by sealing a liquid crystal injection port.

The liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the applied voltage was 5.5 V square wave, and the measurement frequency was 60 Hz by the Toyo Technica Co., Ltd. liquid crystal voltage retention measuring system VHR-1A type (brand name). As a result of measuring the voltage retention, the voltage retention was 97%. In addition, a voltage retention is a value represented by following formula (1) here.

<Equation 1>

Voltage retention (%) = (liquid crystal cell potential difference after 16.7 milliseconds) / (voltage applied at 0 milliseconds) × 100

If the voltage retention of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot keep the applied voltage at a predetermined level for a time of 16.7 milliseconds and cannot align the liquid crystal sufficiently, and such a liquid crystal cell may cause "baking". Is high.

Example  22 and 23 and Comparative example  4

In the "production of a two-component curable resin composition" of Example 21, the types and amounts shown in Table 7 were used as the (A '), components, and (E) components, respectively, except for those used in Table 7 as solvents. The composition was prepared and evaluated in the same manner as in Example 21. The evaluation results are shown in Table 7.

In addition, abbreviated-name which shows each component in Table 7 respectively means the following.

(E) component

E-1: bisphenol A novolak-type epoxy resin (brand name: Epicoat 157S65, Yuka Shell Epoxy Co., Ltd. product)

E-2: bisphenol A type epoxy resin (brand name: Epicoat 828, Yuka Shell Epoxy Co., Ltd. product)

menstruum

S-1: Propylene Glycol Monomethyl Ether Acetate

S-2: diethylene glycol dimethyl ether

(IV) Preparation and Evaluation of Third Composition

Synthesis of Polymer

Synthesis Example  7

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 5 parts by weight of tetraethylthiuram disulfide (molecular weight control agent) and diethylene glycol diethyl in a flask equipped with a cooling tube and a stirrer 200 parts by weight of ether was added, followed by nitrogen replacement by adding 50 parts by weight of glycidyl methacrylate, 20 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl and 30 parts by weight of methacrylic acid, The reaction solution was heated to 70 ° C while stirring slowly, and maintained at this temperature to polymerize for 6 hours. Thereafter, 3 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was added to obtain a solution containing polymer (A-7). Polymer (A-7) had Mw = 11,000 and Mw / Mn = 1.40.

Synthesis Example  8

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 5 parts by weight of tetraethylthiuram disulfide (molecular weight control agent), and propylene glycol monomethyl ether in a flask equipped with a cooling tube and a stirrer. 200 parts by weight of acetate, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of methacrylic acid, 10 parts by weight of styrene and 10 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl After substitution, the reaction solution was heated to 70 ° C. while gradually stirring, and maintained at this temperature to polymerize for 6 hours. Thereafter, 3 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was added to obtain a solution containing polymer (A-8). Polymer (A-8) had Mw = 9,500 and Mw / Mn = 1.55.

Synthesis Example  9

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 5 parts by weight of tetraethylthiuram disulfide (molecular weight control agent) and propylene glycol monomethyl ether in a flask equipped with a cooling tube and a stirrer 200 parts by weight of acetate was added. Subsequently, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of 1-ethylcyclohexyl methacrylate, 10 parts by weight of styrene, and 10 parts by weight of N-cyclohexylmaleimide were substituted for nitrogen, and then the reaction solution was gradually stirred. It heated up at 70 degreeC, maintained this temperature, and superposed | polymerized for 6 hours. Thereafter, 3 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was added to obtain a solution containing polymer (A-9). Polymer (A-9) had Mw = 10,500 and Mw / Mn = 1.60.

compare Synthesis Example  4

6 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer, followed by glycidyl methacrylate 50 20 parts by weight of 20 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl and 30 parts by weight of methacrylic acid were added and substituted with nitrogen, followed by gradually stirring to raise the temperature of the reaction solution to 70 ° C. The solution containing polymer (a-4) was obtained by maintaining this temperature and superposing | polymerizing for 5 hours. The polystyrene reduced weight average molecular weight (Mw) of the polymer (a-4) was 15,000, and molecular weight distribution (Mw / Mn) was 2.4.

Example  24

One component  Preparation of Curable Resin Composition

Bisphenol A novolac as the component (A ') in an amount corresponding to 100 parts by weight of the solid content of the copolymer (A-7) of the solution containing the polymer (A-7) obtained in Synthesis Example 7 above 10 parts by weight of a type epoxy resin (trade name: Epicoat 157S65, manufactured by Yuka Shell Epoxy Co., Ltd.), (G) benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate 1 as an acid generator. 15 parts by weight of γ-glycidoxypropyltrimethoxysilane as an adhesion aid and 0.1 part by weight of SH-28PA (manufactured by Toray Dow Corning Silicon Co., Ltd.) as a surfactant, and the solid content concentration was 20% After further adding propylene glycol monomethyl ether acetate, the composition solution was prepared by filtration with a Millipore filter having a pore size of 0.5 μm. The appearance of this composition solution was colorless and transparent.

One component  Evaluation of Curable Resin Composition

It evaluated like Example 21 except having used the one-component curable resin composition prepared above as a composition solution. The results are shown in Table 8.

Example  25 and 26 and Comparative example  5

In the "Manufacture of one-component curable resin composition" of the said Example 24, it carried out similarly to Example 24 except having used the kind and quantity shown in Table 8 as (A ') component, and using the thing of Table 8 as a solvent. The composition was prepared and evaluated. The evaluation results are shown in Table 8.

In addition, the abbreviation of the solvent column in Table 8 is the same as that of Table 7.

(V) Preparation and Evaluation of Compositions Containing (A'1) Polymers

Synthesis Example  10

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 5 parts by weight of tetraethylthiuram disulfide as a molecular weight control agent, and diethylene glycol diethyl ether in a flask equipped with a cooling tube and a stirrer. 200 parts by weight was added, and then 40 parts by weight of glycidyl methacrylate, 40 parts by weight of 1- (cyclopentyloxy) ethyl methacrylate, 10 parts by weight of styrene and 10 parts by weight of N-cyclohexylmaleimide were added to replace the nitrogen. After slowly stirring was started. After raising the temperature of the solution to 70 ° C. and maintaining the temperature for 5 hours, 2 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, followed by further stirring at 70 ° C. for 2 hours. The solution containing copolymer (A-10) was obtained. Mw of the obtained copolymer (A-10) was 8,000 and molecular weight distribution (Mw / Mn) was 1.60.

Example  27

Preparation and Evaluation of the Fourth Composition

One component  Preparation of Curable Resin Composition

An amount corresponding to 100 parts by weight of the solid content of the copolymer (A-10) of the solution containing the polymer (A-10) obtained in Synthesis Example 10 as the component (A '), and the bisphenol A novolac type as the component (E). 10 parts by weight of an epoxy resin (trade name: Epicoat 157S65, manufactured by Yuka Shell Epoxy Co., Ltd.), 1 part by weight of benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate as an acid generator, and adhesion 15 parts by weight of γ-glycidoxypropyltrimethoxysilane as an adjuvant and 0.1 parts by weight of SH-28PA (manufactured by Toray Dow Corning Silicon Co., Ltd.) as a surfactant, and propylene glycol mono so as to have a solid content concentration of 20%. After further adding methyl ether acetate, the composition solution was prepared by filtration through a Millipore filter having a pore size of 0.5 mu m. The appearance of this composition solution was colorless and transparent.

One component  Evaluation of Curable Resin Composition

It evaluated like Example 21 except having used the one-component curable resin composition manufactured above. The result was as follows.

Transparency: 99%

Heat-resistant dimensional stability: 99%

Heat discoloration resistance: 3%

Surface hardness: 6H

Dynamic micro hardness

 23 ℃: 29

 140 ℃: 25

Adhesion

Si0 ₂ : 100

 Cr: 100

Planarization capacity: 200 nm

Sublimation: None

Voltage retention: 97%

According to the present invention, it is possible to provide a curable resin composition having high radiation sensitivity, sufficiently high resolution, excellent adhesion to a substrate or a base or an upper layer, and suppressing generation of a sublimation during firing of the film forming process.

Claims (18)

(A) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of polystyrene conversion measured by gel permeation chromatography, polymerized by living radical polymerization in the presence of the compound represented by the following formula (1). ) Is 1.7 or less and contains the polymer which has a carboxyl group, The curable resin composition characterized by the above-mentioned. <Formula 1>

Wherein two Z's each independently represent a hydrogen atom, a carboxyl group, a group -R, a group -OR, a group -NR ₂ , a group -COOR, a group -C (= 0) NR ₂ , and a group -P (= 0) R ₂ , a group -P (= O) (OR) ₂ or a group -NRNR-C (= O) R, R is independently a halogen atom, cyano group, hydroxyl group, alkyl group having 1 to 20 carbon atoms, 2 to 20 carbon atoms Is an alkenyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a monovalent heterocyclic group having 3 to 20 atoms in total having a carbon atom and a hetero atom, and R is an alkyl group, an alkenyl group, or an aryl group , In the case of an aralkyl group or a heterocyclic group, one or more of hydrogen atoms of R may be substituted with a halogen atom, cyano group, hydroxyl group or carboxyl group.) The curable resin composition according to claim 1, wherein the polymer (A) has a structure represented by the following general formula (1a). <Formula 1a>

(Wherein Z is the same as that in Formula 1). The curable resin composition according to claim 1, further comprising (B) a polymerizable unsaturated compound and (C) a radiation sensitive polymerization initiator, and used for formation of a spacer. The curable resin composition according to claim 1, further comprising (D) 1,2-quinonediazide compound and used for forming an interlayer insulating film or microlens. Curable resin composition of Claim 1 which further contains (E) cationically polymerizable compound and is used for formation of a protective film. (A ') The ratio (Mw /) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of polystyrene conversion measured by gel permeation chromatography to be polymerized by living radical polymerization in the presence of the compound represented by the formula (1). Curable resin composition whose Mn) is 1.7 or less, contains the polymer which has an oxiranyl group or an oxetanyl group, and (E) cationically polymerizable compound, and is used for formation of a protective film. The curable resin composition according to claim 6, wherein the polymer (A ') has a structure represented by Chemical Formula 1a. The curable resin composition according to any one of claims 5 to 7, further comprising (F) a curing agent or (G) acid generator. A two-component curable resin composition comprising the first liquid which is the curable resin composition according to any one of claims 5 to 7, and a second liquid containing a (F) curing agent. At least (1) Process of forming film of curable resin composition of Claim 3 on board | substrate, (2) exposing radiation to at least a portion of the film; (3) developing the film after exposure, and (4) The process of heating the film after image development Method for forming a spacer, characterized in that the step of carrying out in the order described. A spacer formed by the method of claim 10. It comprises the spacer of Claim 11, The liquid crystal display element characterized by the above-mentioned. At least (1) Process of forming film of curable resin composition of Claim 4 on board | substrate, (2) exposing radiation to at least a portion of the film; (3) developing the film after exposure, and (4) The process of heating the film after image development Method for forming an interlayer insulating film or microlens, characterized in that in the order described. An interlayer insulating film or microlens formed by the method according to claim 13. At least (1) forming a film of the curable resin composition according to any one of claims 5 to 7 on a substrate, and (2) heating the film The protective film forming method characterized by the above-mentioned. The protective film formed by the method of Claim 15. At least (1) mixing the first liquid and the second liquid according to (9); (2) forming a film of the mixed liquid on a substrate, and (3) heating the film The protective film forming method characterized by the above-mentioned. The protective film formed by the method of Claim 17.

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