JP3268771B2 - Photopolymerizable unsaturated compound, method for producing the same, and alkali-soluble radiation-sensitive resin composition using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel photopolymerizable unsaturated compound, a method for producing the same, and an alkali-soluble radiation-sensitive resin composition using the same. For more information,
The present invention provides a photopolymerizable unsaturated compound useful as a photopolymerizable component in an alkali-soluble radiation-sensitive resin composition suitably used for various applications, a method for efficiently producing the compound, It contains a polymerizable unsaturated compound and gives a cured film with excellent heat resistance, transparency, adhesion, chemical resistance, etc., color filters, liquid crystal display elements, integrated circuit elements,
Alkali-soluble radiation-sensitive resin composition suitable as a material for forming a protective film or an interlayer insulating film of a solid-state imaging device, a binder composition for a color resist, or a solder resist used in manufacturing a printed wiring board. It is.

[0002]

2. Description of the Related Art Conventionally, a screen printing method has been used for forming a protective film or an interlayer insulating film of a color filter, a liquid crystal display device, an integrated circuit device, a solid-state image sensor, or the like, or a resist pattern of a printed wiring board. However, this screen printing method is becoming incompatible with recent high-density devices. For this reason, dry film type photoresists and liquid resists have been proposed, but in the case of dry film type photoresists, air bubbles are easily generated during thermocompression bonding, and heat resistance and adhesion are not sufficient, and cost is low. There were problems such as costly.
On the other hand, in the case of a liquid resist, sticking occurs after pre-baking, which causes mask dirt. Therefore, there is a problem that a contact exposure method that is advantageous for improving the contrast of a pattern shape cannot be applied. And, what is currently commercially available, because it uses an organic solvent as a developer, on where there is the air pollution, the solvent is expensive. In addition, Japanese Unexamined Patent Publication
Japanese Patent Application Laid-Open No. 1-243869 discloses a radiation-sensitive resin composition which can be developed with a weak alkaline aqueous solution containing a phenol novolak resin as a main component, but it cannot sufficiently withstand high-temperature, acidic and alkaline conditions. After the treatment, there is a problem that the adhesion to the substrate is reduced. Then, in order to solve such a problem, a photopolymerizable compound having a fluorene skeleton whose cured product is excellent in transparency and heat resistance has recently been proposed. However, although this photopolymerizable compound can solve the above-mentioned problems to some extent by using it, it does not sufficiently satisfy the required performance. For example, JP-A-4-34567
No. 3 , JP-A-4-355450 , JP-A-4-355
Japanese Patent No. 363311 discloses a heat-resistant liquid resist and a color filter material using a reaction product of an epoxy acrylate having a bisphenol fluorene structure and an acid anhydride. To cause mask contamination,
In addition to the problem that the contact exposure method that is advantageous for improving the contrast of the pattern shape cannot be applied, there is a problem that the alkali solubility of the cured product is increased due to an increase in the carboxyl group content, and the developability is poor. Furthermore, the epoxy resin disclosed in Japanese Patent Application Laid-Open No. 4-345,673 has a disadvantage that its solubility is lower than that of an ordinary organic solvent, and the solvent is limited and the film thickness is difficult to be used as a liquid resist. There is. In addition, when a coating film formed by printing or solid coating with a roll coater is thermally cured, sticking remains after the solvent is removed by pre-baking, resulting in poor workability. On the other hand , JP-A-6-1938 and JP-A-7-31
No. 22 discloses that an epoxy acrylate compound having a bisphenol fluorene structure, an acid anhydride, and an acid dianhydride are simultaneously reacted to increase the molecular weight,
General formula [6] obtained by introducing a carboxyl group

Embedded image (X in the formula is the formula

Embedded image A group represented by Y, a residue of the acid anhydride except for the acid anhydride group, Z is a residue of the acid dianhydride except for the acid anhydride group,
m and k each indicate the degree of polymerization, and are 1 / m / k molar ratio.
/ 99 to 90/10) are disclosed. However, when this compound is used, although sticking after pre-baking is eliminated, in this compound, since the acid anhydride not only reacts with the hydroxyl group of the epoxy acrylate but also participates in the condensation reaction, the molecular weight and the acid value are reduced. It is difficult to control the film thickness. As a result, at the same solid concentration, the solution viscosity of the resist increases, so that not only the workability at the time of dissolving, filtering, or applying the solid deteriorates, but also the film thickness in the substrate surface due to the deterioration of the coating characteristics. There is a concern that a problem may occur in that the development characteristics may vary. In addition, Japanese Patent Application Laid-Open
Japanese Patent No. 325494 discloses an epoxy acrylate compound having a bisphenol fluorene structure and a composition containing a carboxyl group-containing alternating copolymer as a main component by reacting only an acid dianhydride. ,
There is a concern that a large amount of unreacted epoxy acrylate compound remains, which lowers water resistance, solvent resistance, and alkali solubility. In order to reduce the amount of unreacted epoxy acrylate compound, it is preferable to increase the use ratio of the acid dianhydride. However, in this case, since the molecular weight is increased, the solution viscosity is increased, and the workability is likely to be significantly deteriorated.

[0003]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a photopolymerizable unsaturated compound which does not have the above-mentioned drawbacks and whose molecular weight can be easily controlled. Method, and containing the photopolymerizable unsaturated compound, the coating film becomes sticking free after pre-baking, the cured film after light irradiation heat resistance, transparency, adhesion, hardness,
An object of the present invention is to provide a radiation-sensitive resin composition which is excellent in chemical resistance and the like, can be developed with a weak alkaline aqueous solution, and is easily adjusted in viscosity so as to have an appropriate solution viscosity.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that an epoxy acrylate having a bisphenolfluorene skeleton is reacted with tetracarboxylic dianhydride to form an oligomer. After that, by using a two-step reaction of blocking the terminal hydroxyl group with a dicarboxylic anhydride, a novel photopolymerizable unsaturated compound having a carboxyl group that does not have the above-described disadvantage and that can easily control the molecular weight can be obtained. And the composition containing this photopolymerizable unsaturated compound, a compound having an epoxy group, a photopolymerization initiator and / or a photosensitizer,
They have found that the radiation-sensitive resin composition can be adapted to the purpose, and have completed the present invention based on this finding. That is, the present invention provides (1) a general formula [1]

Embedded image (X in the formula is the formula

Embedded image A group represented by Y, a residue obtained by removing an acid anhydride group of dicarboxylic anhydride, Z is a residue obtained by removing an acid anhydride group of tetracarboxylic dianhydride, and n is an integer of 1 to 20. (2) a photopolymerizable unsaturated compound represented by the formula [2]:

Embedded image By reacting acrylic acid with the epoxy compound represented by
Equation [3]

Embedded image After obtaining an acrylate derivative represented by the following formula,

Embedded image (Wherein Z has the same meaning as described above), and then reacted with a general formula [5]

Embedded image (Wherein Y has the same meaning as described above), characterized by reacting a dicarboxylic anhydride represented by the general formula [1]:

Embedded image (Wherein X, Y, Z and n in the formula have the same meanings as described above), (3)
(A) the photopolymerizable unsaturated compound according to item 1, (B) a compound having an epoxy group, (C) a photopolymerization initiator and / or
Or an alkali-soluble radiation-sensitive resin composition containing a photosensitizer, and (4) at least one kind selected from (D) a photopolymerizable monomer and an oligomer. 4.) The alkali-soluble radiation-sensitive resin composition according to item 3, wherein the composition is contained in an amount of 50 parts by weight or less per 100 parts by weight of the component.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The photopolymerizable unsaturated compound of the present invention has the general formula [1]

Embedded image (Wherein X, Y, Z and n have the same meanings as described above), which has a structure in which hydroxyl groups at both ends are blocked by dicarboxylic anhydride. Substantially no acid anhydride residue in the polymer chain. On the other hand, the known photopolymerizable unsaturated compound represented by the general formula [6] does not necessarily have a dicarboxylic anhydride residue in the polymer chain and the terminal hydroxyl group is blocked by the dicarboxylic anhydride. Absent. The manufacturing method is also different from the method of the present invention described below. The photopolymerizable unsaturated compound represented by the general formula [1] can be produced very efficiently according to the method of the present invention described below. In the method of the present invention, first, the formula [2]

Embedded image Acrylic acid is reacted with the epoxy compound represented by the formula [3] according to a conventional method,

Embedded image To produce an acrylate derivative represented by the formula: The epoxy compound represented by the above formula [2] can be easily obtained, for example, by reacting bisphenolfluorene with epihalohydrin such as epichlorohydrin. Next, the acrylate derivative represented by the formula [3] thus obtained is added to the general formula [4] in a suitable solvent.

Embedded image (Wherein Z in the formula has the same meaning as described above), and then reacted with a general formula [5]

Embedded image (Wherein Y has the same meaning as described above). The solvent is not particularly limited as long as it can dissolve each component and the reaction product used in the reaction and is inert to the reaction, and is not particularly limited. Examples thereof include cellosolves such as ethyl cellosolve acetate and butyl cellosolve acetate. Solvents can be preferably used. The reaction temperature is preferably such that the tetracarboxylic dianhydride and dicarboxylic anhydride react quantitatively with the hydroxyl group in the acrylate derivative of the formula [3]. Is usually selected in the range of 100 to 130 ° C., preferably 115 to 125 ° C., and in the reaction with dicarboxylic anhydride, it is usually selected in the range of 80 to 110 ° C., preferably 80 to 90 ° C. You.

[0006] In the reaction of tetracarboxylic dianhydride with an acrylate derivative, if the reaction temperature exceeds 130 ° C, polymerization of the acrylate derivative partially occurs, causing a sudden increase in the molecular weight.
If it is less than 3, the reaction does not proceed smoothly, and unreacted tetracarboxylic dianhydride may remain. On the other hand, in the reaction between the dicarboxylic anhydride and the acrylate derivative, if the reaction temperature exceeds 110 ° C., condensation between the carboxyl group and the hydroxyl group occurs, which causes an increase in the molecular weight. Does not progress to
Unreacted dicarboxylic anhydride may remain.
In this reaction, the total amount of the acid anhydride groups in the tetracarboxylic dianhydride and the dicarboxylic anhydride is usually 60 to 100 mol parts, preferably 75 mol parts, based on 100 mol parts of the hydroxyl groups of the acrylate derivative. More than 100
It is advantageous to carry out the reaction in a proportion of less than a molar part. Here, the acid anhydride group is a -co-o-co- group, and it is defined that 50 mol parts of tetracarboxylic dianhydride corresponds to 100 mol parts of dicarboxylic anhydride.
If the total amount of the acid anhydride groups is less than 60 parts by mole, it is difficult to sufficiently increase the molecular weight to sufficiently introduce the polymerizable double bond group required for high sensitivity, and if the amount exceeds 100 parts by mole, Similarly, not only does the molecular weight increase not be obtained, but also unreacted tetracarboxylic dianhydride and dicarboxylic anhydride remain, which causes deterioration in developability. Also, the ratio of dicarboxylic anhydride and tetracarboxylic dianhydride,
The molar ratio is usually 1:99 to 90:10, preferably 5:90.
It is selected in the range of 95 to 80:20. When the proportion of dicarboxylic anhydride is less than 1 mol% of the total anhydride, not only does the resin viscosity increase and the workability deteriorates, but also the unexposed part dissolves in the developing solution because the molecular weight becomes too large. Without this, the desired pattern cannot be obtained. On the other hand, if the proportion of dicarboxylic anhydride exceeds 90 mol% of the total anhydride, the molecular weight is small, so that sticking remains in the coating film after prebaking. Examples of the tetracarboxylic dianhydride represented by the general formula [4] include, for example, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride,
Aromatic polycarboxylic anhydrides such as biphenyltetracarboxylic dianhydride and biphenylethertetracarboxylic dianhydride are exemplified. Examples of the dicarboxylic anhydride represented by the general formula [5] include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
Examples include methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride and the like.

[0007] The molecular weight and acid value of the photopolymerizable unsaturated compound represented by the general formula [1] of the present invention can be determined by adding the acrylate derivative represented by the formula [3] in the above reaction step.
When reacting the tetracarboxylic dianhydride represented by the general formula [4], it can be substantially controlled by controlling the reaction conditions and changing the value of n in the general formula [1]. Here, n is an integer in the range of 1 to 20.
Next, the alkali-soluble radiation-sensitive resin composition of the present invention comprises (A) a photopolymerizable unsaturated compound represented by the general formula [1], (B) a compound having an epoxy group, C)
It contains a photopolymerization initiator and / or a photosensitizer. In the present invention, one of the above-mentioned photopolymerizable unsaturated compounds as the component (A) may be used alone, or two or more may be used in combination. Examples of the compound having an epoxy group as the component (B) include phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and biphenyl epoxy resin. Epoxy resins such as alicyclic epoxy resins, phenylglycidyl ether, p-
Compounds having at least one epoxy group, such as butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, glycidyl methacrylate, and the like are included. One of these may be used alone, or two or more may be used in combination. On the other hand, as the photopolymerization initiator and the photosensitizer of the component (C), for example, acetophenone,
2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p
Acetophenones such as -tert-butylacetophenone, benzophenone, 2-chlorobenzophenone,
Benzophenones such as p, p'-bisdimethylaminobenzophenone, and benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether;
Benzyldimethyl ketal, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene,
Sulfur compounds such as 2-methylthioxanthene and 2-isopropylthioxanthene; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; and azobisisobutyronitrile And organic peroxides such as benzoyl peroxide and cumene peroxide; and thiol compounds such as 2-mercaptobenzimidal, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole. One of these compounds may be used alone, or two or more thereof may be used in combination. In addition, a compound which does not act as a photopolymerization initiator by itself, but which can increase the ability of the photopolymerization initiator by using in combination with the above compound, can be added. Such compounds include, for example, tertiary amines such as triethanolamine, which are effective when used in combination with benzophenone.

The content ratio of each component in the radiation-sensitive resin composition of the present invention is 5 to 50 parts by weight of the component (B) and 0.5% by weight of the component (C) per 100 parts by weight of the component (A).
It is preferable that the content is 1 to 30 parts by weight, particularly 10 to 30 parts by weight of the component (B) and 1 to 2 parts by weight of the component (C).
It is preferred to contain it in a proportion of 0 parts by weight. (A) Component 1
When the content of the component (B) is less than 5 parts by weight per 100 parts by weight, the properties of the composition of the present invention after curing, particularly the alkali resistance, become insufficient. Cracks occur during curing, and the adhesion tends to decrease. When the content of the component (C) is less than 0.1 part by weight per 100 parts by weight of the component (A), the speed of photopolymerization is reduced, and the sensitivity is reduced. On the other hand, when the amount exceeds 30 parts by weight, the light does not easily reach the substrate, so that the adhesion between the substrate and the resin deteriorates. In the resin composition of the present invention, if necessary, a monomer or oligomer which can be polymerized by light can be contained as a component (D) according to the physical properties of the intended use. Examples of such a monomer or oligomer polymerizable by light include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate; Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Acrylate, it can be mentioned dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate of a (meth) acrylic acid esters. One of these monomers and oligomers may be used alone, or two or more thereof may be used in combination.
The monomer or oligomer as the component (D) functions as a viscosity modifier or a photocrosslinking agent, and the amount of the monomer or oligomer can be appropriately selected within a range that does not impair the properties of the resin composition of the present invention. Usually, at least one of the above monomers and oligomers is blended in an amount of 50 parts by weight or less based on 100 parts by weight of the photopolymerizable unsaturated compound as the component (A). If the amount of the monomer or oligomer exceeds 50 parts by weight, a problem may occur in the sticking property after prebaking.

In the radiation-sensitive resin composition of the present invention, if necessary, for example, an epoxy group curing accelerator, a thermal polymerization inhibitor, an antioxidant, and an adhesion aid may be used as long as the object of the present invention is not impaired. And additives such as a surfactant and an antifoaming agent. Examples of the epoxy group curing accelerator include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts or methylol group-containing compounds, and the like. In addition, various properties such as heat resistance, solvent resistance, acid resistance, plating resistance, adhesion, electrical properties and hardness of the obtained resist film can be improved. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and phenothiazine. Further, by adding the adhesion aid, the adhesiveness of the obtained composition is improved. As the adhesion aid, preferably, a silane compound having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group (functional silane coupling agent) is used. Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-glycol. Sidoxypropyltrimethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Further, examples of the defoaming agent include silicone-based, fluorine-based, and acrylic-based compounds. Further, by adding a surfactant, the obtained composition is easily applied, and the flatness of the obtained film is also improved. Examples of the surfactant include BM-1000 (manufactured by BM Hemy), Megafax F142D, F172, F173, and F183.
[Dainippon Ink Chemical Industry Co., Ltd.], Florad FC-1
35, FC-170C, Florado FC-430 and FC-431 (manufactured by Sumitomo 3M Limited), Surflon S-112, S-113, S-131, S-1
41 and S-145 [manufactured by Asahi Glass Co., Ltd.], SH-28
PA, SH-190, SH-193, SZ-6032,
Fluorinated surfactants such as SF-8428, DC-57 and DC-190 [manufactured by Toray Silicone Co., Ltd.].

The radiation-sensitive resin composition of the present invention comprises the above components (A), (B), (C), and optionally (D) and other additives, which are usually added to an organic solvent. It can be prepared by dissolving and mixing uniformly. The organic solvent is not particularly limited as long as it does not react with each component in the composition and dissolves with each other, and is not particularly limited. Examples thereof include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycol monomethyl ether, diethylene glycol diethyl ether; Diethylene glycol dimethyl ether,
Diethylene glycols such as diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether;
Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-
Ketones such as hydroxy-4-methyl-2-pentanone; if ぴ is ethyl 2-hydroxypropionate,
Methyl hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-2-
Methyl methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate,
Esters such as acetyl acetate, butyl acetate, methyl lactate and ethyl lactate are exemplified.

Among them, glycol ethers, alkylene glycol alkyl ether acetates, diethylene glycol dialkyl ethers, ketones and esters are preferred, and ethyl 3-ethoxypropionate, ethyl lactate and propylene glycol monomethyl ether acetate are particularly preferred. , Ethylene glycol monoethyl ether acetate and methyl amyl ketone. One of these solvents may be used alone,
Two or more kinds may be used as a mixture. The composition of the present invention thus prepared is usually, for example, having a pore size of 1.0 to 0.2.
It is used after being filtered through a millimeter filter of about μm. As a method for applying the solution of the radiation-sensitive resin composition of the present invention to a substrate, any method such as a dipping method, a spray method, a roller coater, a slit coater, a bar coater, and a spinner may be used. Can be. By applying the resin composition solution to a thickness of about 1 to 30 μm by these methods and removing the solvent, a film is formed. Radiation used in the radiation-sensitive resin composition of the present invention may be, in order of wavelength, visible light, ultraviolet light, electron beam, X-ray, α-ray, β-ray, γ-ray, or the like. it can. Of these, ultraviolet rays are the most preferable radiation in terms of economy and efficiency. Ultraviolet light oscillated from a lamp such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or an arc lamp or a xenon lamp can be suitably used as the ultraviolet light used in the present invention. The radiation having a shorter wavelength than ultraviolet radiation has high chemical reactivity and is theoretically superior to ultraviolet radiation, but ultraviolet radiation is practical from the viewpoint of economy.

The photosensitive layer made of the resin composition provided on the substrate is selectively exposed using the above-described radiation, and then subjected to a developing treatment using a developing solution to remove a non-irradiated portion of the radiation to form a thin film. Is performed. Examples of the developing method include a puddle method, a dipping method, and a rocking immersion method. Examples of the developer include an alkaline aqueous solution, a mixed solution of an alkaline aqueous solution and a water-soluble organic solvent and / or a surfactant, and an organic solvent in which the composition of the present invention is dissolved. It is a mixture with the agent. Examples of the base used for preparing an alkaline aqueous solution suitable for developing the radiation-sensitive resin composition of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, and engineered amine. N-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0]
-7-untecene, 1,5-diazabicyclo [4,3,
0] -5-nonane, preferably sodium carbonate and tetramethylammonium hydroxide. Examples of the water-soluble organic solvent include methanol, ethanol, and acetone. The development of the resin composition of the present invention can be carried out at a temperature of usually 10 to 50 ° C., preferably 20 to 40 ° C. using a commercially available developing machine or ultrasonic cleaning machine.

After the alkali development, it is desirable to carry out an epoxy curing treatment by heating in order to improve the alkali resistance. In the resin composition of the present invention, by performing the heat treatment, not only the durability against strong alkaline water is remarkably improved, but also various properties such as glass, adhesion to metals such as copper, heat resistance, and surface hardness. improves. The heating temperature and the heating time under the heat curing conditions include, for example, 80 to 200 ° C. and 10 to 120 minutes, respectively. Next, an example of a method for producing a coating by photopolymerization of the radiation-sensitive resin composition of the present invention will be described. First, a resist solution comprising the resin composition is coated on a substrate by an arbitrary method. In the embodiment, spin coating is used, but of course, a coating method such as dip coating, bar coating, roll coating, slit coating and the like is also possible. After coating the resist solution, pre-bake is performed to evaporate the solvent. Next, contact exposure is performed using an ultra-high pressure mercury lamp or the like, and the unexposed portions are developed with an aqueous solution of about 1% by weight of sodium carbonate and further washed with water. And
The coating is completely dried by post-baking at a temperature of about 200 ° C, and the desired heat resistance, transparency, adhesion, hardness,
A coating film having excellent solvent resistance, alkali resistance and the like can be obtained. The radiation-sensitive resin composition of the present invention is useful as an insulating film, an insulating paint, an adhesive, a printing ink, a coating agent, and the like, particularly as a color filter material used for a liquid crystal display device or a solid-state imaging device. The cured product has excellent hardness, solder heat resistance, transparency, acid resistance, alkali resistance, solvent resistance, insulation resistance, electrolytic corrosion resistance, and plating resistance. Shows smoothness and adhesion to substrates. For example, as a material for a color filter, by blending a leveling agent or the like with the resin composition of the present invention, it can be suitably used as a protective film for a color filter. In this case, it is possible to sputter ITO (indium tin oxide) on the protective film at a high temperature of 250 ° C. (200 ° C. is the highest temperature because the conventional protective film has no heat resistance), and It can withstand strong acid and strong alkali treatment at the time of patterning. Also,
By mixing the above composition with a pigment or carbon black, it can be suitably used as a color resist ink or a resist ink for a black matrix, respectively. In this case, a known organic pigment or inorganic pigment can be used as the pigment.

[0014]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 In a 500 mL four-necked flask, 235 g (epoxy equivalent: 235) of bisphenolfluorene type epoxy resin and 110 mg of tetramethylammonium chloride, 2,6-
100 mg of di-tertbutyl-4-methylphenol and 72.0 g of acrylic acid were charged, and heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 mL / min. Next, the temperature was gradually raised while the solution was cloudy,
The mixture was heated to 120 ° C. and completely dissolved. Here, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target. Then, the mixture was cooled to room temperature to obtain a colorless, transparent, and solid bisphenolfluorene-type epoxy acrylate represented by the formula [3]. Next, 600 g of propylene glycol monomethyl ether acetate was added to 307.0 g of the above-obtained bisphenolfluorene-type epoxy acrylate and dissolved, and then 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was mixed, gradually heated, and reacted at 110 to 115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain a compound 1 of the general formula [1] (in the formula, Y / Z molar ratio = 50.0
/50.0). The disappearance of the acid anhydride was confirmed by an IR spectrum. Example 2 Using 307.0 g of the bisphenolfluorene-type epoxy acrylate produced in Example 1, 600 g of propylene glycol monomethyl ether acetate was added to form a solution, and then 104.7 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide. Were mixed and gradually heated to react at 110 to 115 ° C. for 4 hours. After confirming disappearance of the acid anhydride group, 1,2,3,6
-Mixing 15.2 g of tetrahydrophthalic anhydride, 90
The mixture was reacted at 6 ° C. for 6 hours to obtain a compound 2 of the general formula [1] (Y / Z molar ratio in the formula = 23.5 / 76.5). The disappearance of the acid anhydride was confirmed by IR spectrum in the same manner as in Example 1 above.

Embodiment3  Bisphenol fluorene type epoxy produced in Example 1
Using 307.0 g of acrylate, propylene glycol
And add 600 g of monomethyl ether acetate
Benzophenone tetracarboxylic dianhydride
96.6 g and 1 g of tetraethylammonium bromide are mixed.
The mixture was gradually heated and reacted at 110 to 115 ° C for 4 hours.
I let you. After confirming the disappearance of the acid anhydride group, 1,2,3,6
-45.6 g of tetrahydrophthalic anhydride were mixed, and 90
The compound represented by the general formula [1]3
(Y / Z molar ratio in the formula = 50.0 / 50.0) was obtained.
The disappearance of the acid anhydride was confirmed by an IR spectrum.

Comparative Example 1 Using 307.0 g of the bisphenol fluorene type epoxy acrylate prepared in Example 1, 600 g of propylene glycol monomethyl ether acetate was added to form a solution, and then 102.3 g of benzophenonetetracarboxylic dianhydride and bromide. 1 g of tetraethylammonium was mixed, the temperature was gradually raised, and the mixture was reacted at 110 to 115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 1,2,3,3
0.5 g of 6-tetrahydrophthalic anhydride is mixed, and 90
The mixture was reacted at 6 ° C. for 6 hours to obtain a compound 4 of the general formula [1] (Y / Z molar ratio in the formula = 0.8 / 99.2). Acid anhydride
Disappearance was confirmed by IR spectrum. Comparative Example 2 After using 307.0 g of the bisphenolfluorene-type epoxy acrylate produced in Example 1 and adding 600 g of propylene glycol monomethyl ether acetate to form a solution, 11.4 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were obtained. Were mixed and gradually heated to react at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 1,2,3,6
103.1 g of tetrahydrophthalic anhydride were mixed, and 9
The reaction was carried out at 0 ° C. for 6 hours to obtain a compound 5 of the general formula [1] (Y / Z molar ratio in the formula = 95.0 / 5.0). The disappearance of the acid anhydride was confirmed by an IR spectrum. Comparative Example 3 Using 307.0 g of the bisphenolfluorene-type epoxy acrylate produced in Example 1, 600 g of propylene glycol monomethyl ether acetate was added to form a solution, and then 80.5 g of benzophenonetetracarboxylic dianhydride, 1,2,3 36.0 g of 1,6-tetrahydrophthalic anhydride and 1 g of tetraethylammonium bromide
It was mixed, gradually heated and allowed to react for 6 hours at 110-115 [° C., to obtain a compound of general formula [6] 6 (Y / Z molar ratio = 50.0 / 50.0 in the formula). The disappearance of the acid anhydride is IR
Confirmed by spectrum. The equivalent ratio and properties during production for compounds 4-6 obtained in Example 1 to the compound obtained in 3 1 3 and Comparative Examples 1 to 3 shown in Table 1.

[0017]

[Table 1]

(Note) 1) Equivalent ratio: bisphenolfluorene type epoxy acrylate / benzophenonetetracarboxylic dianhydride / 1,2,3,3
6-tetrahydrophthalic anhydride 2) Resin acid value: 1 g of a sample is precisely weighed in a 100 ml Erlenmeyer flask, dissolved in 30 ml of acetone, and then dissolved in 0.1 M NaOH aqueous solution using bromothymol blue solution as an indicator. And titrate. 3) Number average molecular weight: It is a converted value measured by a gel permeation chromatography method. 4) solution viscosity: As is apparent from the results in Table 1, except compound 6, since the actual measurement value and the theoretical value of the resin acid value indicates a same value if ho and condensation reaction occurred in the reaction However, it is considered that a compound having a structure represented by the general formula [1] has been obtained. On the other hand, in the synthesis of compound 6 , as shown by the physical property values (decrease in acid value, increase in viscosity), increase in molecular weight due to condensation reaction occurs even when the mixing ratio of acid anhydride / acid dianhydride is the same. This causes the solution viscosity to increase. It has been confirmed that this tendency increases as the reaction time increases. On the other hand, in the present invention, it was not confirmed that the molecular weight increased with time, and it was proved that the production method was stable even in industrialization. Examples 4 to 8 and Comparative Examples 4 and 5 The photopolymerizable unsaturated compounds (compounds 1 to 5 ) obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were used, and the composition shown in Tables 2 and 3 was used. Was prepared.

[0019]

[Table 2]

[0020]

[Table 3]

(Note) 1) Tetramethylbiphenyl type epoxy resin: manufactured by Yuka Shell Co., Ltd., trade name “Epicoat YX-4000”, epoxy equivalent 193 2) Irgacure-907: manufactured by Ciba Specialty Chemicals Co. (1) Formation The resist solution obtained above was applied on a glass substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 120 seconds to form a coating film having a thickness of about 2 μm. (2) Exposure / development treatment A mask having a predetermined pattern is placed on the glass substrate on which the coating film is formed as described above, and ultraviolet light having a light intensity of 9.5 mW / cm ² at a wavelength of 405 nm using a 250 W high-pressure mercury lamp. Was irradiated so as to have an energy amount of 1000 mJ / cm ² . After irradiation, 2% by using 1% by weight aqueous sodium carbonate solution
Developing treatment was performed at 5 ° C. for 30 seconds to remove unexposed portions of the coating film. Thereafter, a rinsing treatment was performed with ultrapure water. (3) Formation of heat-cured film The glass substrate on which the thin film exposed and developed in (2) above was formed was subjected to a post-baking treatment in an oven at 200 ° C. for 30 minutes to heat-cur the thin film (hereinafter, as described below). The cured film is referred to as a heat-cured film).

Various characteristics were determined in the following manner. <Drying property of coating film> In the above (1), the drying property of the coating film after pre-baking was evaluated according to JIS K 5400. The ranking of the evaluation is as follows. ：: no sticking was observed at all, Δ: slight sticking was observed, x: remarkable sticking was observed. <Developability to aqueous alkaline solution> In the above (2), 1% by weight without exposure treatment was used. For 30 seconds in an aqueous solution of sodium carbonate for development. The glass substrate after development was magnified 50 times and the remaining resin was visually evaluated. The ranking of the evaluation is as follows. ：: Good developability (no resist left on glass) △: Poor developability (resist slightly on glass) ×: Poor developability (residual on glass) (A lot of resist remains) <Exposure sensitivity> In the above (2), a step tablet (a negative mask having an optical density of 12 steps) was brought into close contact with the coating film as a mask, and exposure and development were performed. Thereafter, the number of steps of the remaining step tablet was examined (in this evaluation method, the higher the sensitivity, the larger the number of remaining steps). <Coating film hardness> The hardness of the heat-cured film obtained in (3) above was measured. To
In accordance with the test method of JIS K 5400, the highest hardness at which a coating film was not scratched when a load of 9.8 N was applied using a pencil hardness tester was indicated. The pencil used is "Mitsubishi High Uni". <Adhesion to substrate> At least 100% was added to the heat-cured film obtained in (3) above.
A cross-cut was made so as to make a grid, and then a peeling test was performed using a cellophane tape. The ranking of the evaluation is as follows. ：: No peeling was observed at all, ×: Peeling was observed at all <heat resistance> The heat-cured film obtained in the above (3) was placed in an oven at 250 ° C. for 3 hours, and the state of the coating film was evaluated. . The ranking of the evaluation is as follows. ：: No abnormality in appearance of coating film, ×: Appearance of coating film, peeling and coloring. <Chemical resistance> The heat-cured film obtained in the above (3) was immersed in the following chemicals under the following conditions, and the appearance and adhesion after immersion were evaluated.
The ranking of the evaluation is as follows. ○: No abnormality in appearance of coating film, Δ: Slightly discolored in appearance of coating film, peeling and coloring, ×: Remarkable appearance in coating film,
Peeling, coloring Acid resistance: immersed in 5% by weight HCl aqueous solution for 24 hours at room temperature Alkali resistance: 24% in 5% by weight NaOH aqueous solution at room temperature
Soaking for 4 hours Soaking in 4% by weight KOH aqueous solution at 50 ° C for 10 minutes Soaking in 1% by weight NaOH aqueous solution at 80 ° C for 5 minutes Solvent resistance: Soaking in N-methylpyrrolidone at 40 ° C for 10 minutes In N-methylpyrrolidone Immersion at 80 ° C. for 5 minutes The results are shown in Table 4 . Comparative Example 4 was developed at the time of development.
Because unexposed parts did not dissolve and patterning was not possible,
Subsequent evaluations were discontinued.

[0023]

[Table 4]

As is clear from the results in Table 4 , Example 4
No. to No. 8 were able to achieve the desired physical properties. However, when the molar ratio of Y / Z = 0.8 / 99.2 as in Comparative Example 4, the molecular weight of the resin becomes too large, so that the unexposed portion does not dissolve in the developing solution and the target pattern is not obtained. I can't get it. Further, in the case of the molar ratio of Y / Z = 95/5 as in Comparative Example 5, Comparative Example 4
Conversely, since the molecular weight of the resin becomes too small, the sticking phenomenon after prebaking is remarkable, and a problem remains in the drying property of the coating film. From the above results, the radiation-sensitive resin composition of the present invention has heat resistance, transparency, adhesion, hardness, solvent resistance,
It has been found that a protective film having excellent alkali resistance and the like can be provided.

[0025]

The photopolymerizable unsaturated compound of the present invention is a novel compound, and is useful as a photopolymerizable component in an alkali-soluble radiation-sensitive resin composition suitably used for various applications. is there. The radiation-sensitive resin composition of the present invention using this photopolymerizable unsaturated compound is an alkali-soluble radiation-sensitive resin composition excellent in heat resistance and transparency that could not be achieved by the conventional one. Therefore, according to the resin composition of the present invention, there is also an advantage that the coating film becomes sticking-free after the pre-baking, and the contact exposure becomes possible, leading to an increase in resolution. Moreover, the radiation-sensitive resin composition of the present invention has a cured film having acid resistance, alkali resistance,
It is excellent in solvent resistance, surface hardness, etc., so it is useful not only for permanent protection masks such as solder resists, but also for etching resists and interlayer insulating materials related to printed wiring boards, radiation-sensitive adhesives, It can be used in a wide range of fields such as paints, photosensitive liquids for screen printing and resist inks.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ identification code FI C08G 59/42 C08G 59/42 (58) Investigated field (Int.Cl. ⁷ , DB name) C08F 20/30 C07C 67/08 C07C 69/76 C08F 299/02 C08G 59/14 C08G 59/42 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A compound of the general formula [1] (X in the formula is a compound of the formula And n is an integer of 1 to 20; Y is a residue of the dicarboxylic anhydride excluding the acid anhydride group; and Z is a residue of the tetracarboxylic dianhydride excluding the acid anhydride group. Is the base )
A photopolymerizable unsaturated compound represented by the formula:
Anhydride and tetracarboxylic dianhydride in a molar ratio of 1:
It is obtained by reacting at a ratio of 99 to 90:10.
A photopolymerizable unsaturated compound. 2. The formula [2] Reacting an epoxy compound represented by the formula with acrylic acid to obtain a compound of the formula [3] After obtaining an acrylic acid derivative represented by the following formula, this is represented by the general formula [4]. (Wherein Z is a residue of the tetracarboxylic dianhydride except for the acid anhydride group), and then reacted with a tetracarboxylic dianhydride represented by the general formula [5]: (Y in the formula, the dicarboxylic acid is a residue obtained by removing the acid anhydride groups of the anhydride) of a dicarboxylic acid anhydride represented by the deer
Molar ratio of rubonic anhydride to tetracarboxylic dianhydride
And reacting by adding at a ratio of 1:99 to 90:10 in the general formula [1]. (X in the formula is a compound of the formula: Y and Z are the same as described above, and n is 1
Which is an integer of from 20 to 20 ). 3. A photopolymerizable unsaturated compound according to claim 1, (B) a compound having an epoxy group, and (C) a photopolymerization initiator and / or a photosensitizer. And an alkali-soluble radiation-sensitive resin composition. 4. Further, at least one selected from the group consisting of (D) a photopolymerizable monomer and oligomer, (A) Light
The alkali-soluble radiation-sensitive resin composition according to claim 3, which is contained in a proportion of 50 parts by weight or less per 100 parts by weight of the polymerizable unsaturated compound.