JPH05339356A - Photopolymerizable unsaturated compound, and photosensitive resin composition of alkali development type - Google Patents

Abstract

PURPOSE:To obtain the title compd. useful for obtaining the title compsn. excel lent in heat resistance, transparency, resolution, etc., by selecting a compd. having specific structural units and a specified inherent viscosity. CONSTITUTION:The title compd. is selected which has structural units of formula I [wherein R1 and R2 are each H, 1-5C alkyl, or halogen; R3 is H or CH3; X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -C(CH3)2-, -O-, a group of formula II, or a direct bond; Y is an acid anhydride residue; Z is an acid diahydride residue; and (m:n) is (1:99)-(90:10)] and an inherent viscosity (30 deg.C, 0.5g in 100ml of N- methylpyrrolidone) of 0.1dl/g or higher.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable unsaturated compound and an alkali developing type photosensitive resin composition using the same. More specifically, it can be used as a protective film for color filters or as a solder resist in the production of printed wiring boards, and the coating becomes tack-free after pre-curing, which is a step of removing the solvent, and the active energy rays and the photopolymerization initiator cause light The present invention relates to an aqueous alkaline solution-developable photosensitive resin composition capable of forming a permanent protective film excellent in heat resistance, transparency, adhesion, alkali resistance, and solvent resistance by polymerization, and also to such alkali development. The present invention relates to a photopolymerizable unsaturated compound suitable for preparing a photosensitive resin composition.

[0002]

2. Description of the Related Art Conventionally, a screen printing method has been widely used as a method of forming a resist pattern on a protective film and a printed wiring board of this type. When such a screen printing method is used, in many cases, bleeding during printing is performed. Phenomenon such as bleeding or sagging occurs, which makes it difficult to cope with the recent increase in density of printed wiring boards. In order to solve these problems, a dry film type photoresist and a liquid developable resist ink have been proposed, but in the case of a dry film type photoresist, bubbles are easily generated during thermocompression bonding. However, there are problems such as heat resistance and adhesion, and high price.

On the other hand, the liquid resist has a problem in that it has tack after pre-curing, and the contact exposure operation, which is advantageous in increasing resolution and tapering, cannot be applied because it causes contamination of the mask. The commercially available products use an organic solvent as a developing solution, which causes a problem of air pollution and the solvent is expensive.
For example, JP-A-61-243,869 discloses a photosensitive resin composition which can be developed with a weak alkaline aqueous solution containing a phenol novolac resin as a main component. There is a problem that it is not sufficiently durable and the adhesion with the substrate is lowered after the treatment.

[0004]

The object of the present invention is to produce a photopolymerizable unsaturated compound which does not have the above-mentioned drawbacks, and to use it for a photosensitive resin composition, that is, a coating film after pre-curing. Provides a photosensitive resin composition that is tack-free, is capable of contact exposure, and has excellent heat resistance, transparency, adhesion, hardness, solvent resistance, alkali resistance, etc. after light irradiation and that can be developed with a weak alkaline aqueous solution. Especially. In particular, it is intended to provide a photopolymerizable unsaturated compound which can be developed with a weak alkaline aqueous solution and which is suitable for the production of a solder mask or the like in the production of a protective film for a color filter or a printed wiring board, and a photosensitive resin composition using the same. The purpose is.

[0005]

In order to solve such a problem, the present inventors have synthesized a photopolymerizable unsaturated compound having a carboxyl group based on various epoxy acrylates, and prepared it as an epoxy compound. It was found that the object of the present invention can be achieved by using the above together with the present invention, and the present invention has been completed.

That is, the present invention (A) is represented by the following general formula (1), and a solution of 0.5 g of the compound dissolved in 100 ml of N-methylpyrrolidone is measured at 30 ° C. to obtain an inherent viscosity (η). _inh ) is not less than 0.1 dl / g and is a photopolymerizable unsaturated compound.

[Chemical 5] (However, in the formula, R ₁ and R ₂ are any of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a halogen atom,
R ₃ is a hydrogen atom or a methyl group, X is —CO—, —
_{SO 2 -, - C (CF} 3) 2 -, - Si (CH 3)
_{2 -, - CH 2, -C} (CH 3) 2 -, - O- or

[Chemical 6] Or absent, Y represents a residue of an acid anhydride, Z
Represents a residue of an acid dianhydride, and m: n of the number of structural units has a molar ratio of 1/99 to 90/10).

The present invention also provides (A) the above general formula (1)
Containing a photopolymerizable unsaturated compound represented by the formula (B), a compound having an epoxy group, and (C) a photopolymerization initiator or a sensitizer, and the component B and the component C with respect to 100 parts by weight of the component A. The ratio of the components is 5 to 50 parts by weight and 0.1 to respectively.
It is an alkali developing type photosensitive resin composition which is 30 parts by weight. Further, the alkali-developable photosensitive resin composition of the present invention contains 50 parts by weight or less of (meth) acrylic monomer and (meth) per 100 parts by weight of the photopolymerizable unsaturated compound represented by the general formula (1). It further contains at least one kind of acrylic oligomer. Further, in the present invention, R _{1 to} R ₃ in the photopolymerizable unsaturated compound represented by the general formula (1) are preferably hydrogen atoms, and X is

[Chemical 7] Is preferred.

The contents of the present invention will be described in detail below. In the compound represented by the general formula (1), which constitutes the photopolymerizable unsaturated compound (A) (hereinafter, referred to as A component), X
Specific examples of the bisphenol component containing -CO- include bis (4-hydroxyphenyl) ketone and bis (4
- hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, and the like, also, -SO ₂ as X - bis (4-hydroxyphenyl as those containing) Sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone and the like can be mentioned, and further X is —C (CF).
₃ ) _3- containing _3- bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexa Fluoropropane and the like, and X
As -Si (CH _{3) 2} - as containing bis (4-hydroxyphenyl) dimethylsilane, bis (4
-Hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, and the like, and X is -C.
Examples of compounds containing H ₂ − include bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, and the like. further, -C as X (CH _{3) 2} - as containing the 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2 , 2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-)
3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, and the like, and those containing —O— as X include bis (4-hydroxyphenyl) ether and bis ( 4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl ether) and the like can be mentioned, and as X,

[Chemical 8] Include, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3)
-Methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-
Bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3)
-Methoxyphenyl) fluorene, 9,9-bis (4-
Hydroxy-3,5-dimethylphenyl) fluorene,
9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-)
3,5-dibromophenyl) fluorene and the like,
In addition, examples of the absence of X include 4,4′-biphenol and 3,3 ′ biphenol, but the X is not necessarily limited thereto. Also, these may be used as a mixture of any of them.

Further, Y and Z in the general formula (1) are
Each Y represents an acid anhydride residue, and Z represents an acid dianhydride residue. Examples of the acid anhydride compound for introducing Y include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, Examples thereof include chlorendic anhydride, methyltetrahydrophthalic anhydride, and examples of the acid dianhydride compound of Z include pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetra. Examples thereof include aromatic polycarboxylic acid anhydrides such as carboxylic acid dianhydride.

The photopolymerizable unsaturated compound as the component A can be produced as follows. For example, first, by reacting a bisphenolfluorene type epoxy compound synthesized from bisphenolfluorene represented by the following general formula (2) with a (meth) acrylic acid represented by the following general formula (3), A bisphenol fluorene type epoxy acrylate resin represented by the general formula (4) is synthesized, and then heated in a cellosolve solvent such as ethyl cellosolve acetate or butyl cellosolve acetate with an acid anhydride compound which is a mixture of Y and Z described above. Then
It is produced by reacting. As the reaction temperature,
It is desirable that the acid anhydride compound and the epoxy acrylate resin react quantitatively, and the temperature is 100 to 130 ° C, preferably 115 to 125 ° C. This reaction is the same for the entire alkali developable resin of the general formula (1).

[0011]

[Chemical 9]

In the general formula (1), Y represents an acid anhydride residue and Z represents an acid dianhydride residue, and the compound is represented by the general formula (4) bisphenolfluorene type epoxy acrylate. However, the m / n ratio is 1/99 to 90/1 in terms of molar ratio.
0, preferably 5/95 to 80/20. When the proportion of m is less than 1 mol%, the whole carboxyl group (—CO
The amount of OH) is large, the alkali resistance is lost, and the exposed portion is also eluted into the alkaline aqueous solution which is the developing solution, and the desired patterning cannot be obtained. If m is more than 90%, the alkali developability is poor and patterning becomes difficult. Also,
Regarding the molecular weight of the photopolymerizable unsaturated compound, the inherent viscosity (η _inh ) measured at 30 ° C. of a solution prepared by dissolving 0.5 g of this compound in 100 ml of N-methylpyrrolidone is 0.1 dl / g or more, preferably 0.1. It is 15 dl / g or more. If it is less than 0.1 dl / g, the molecular weight is too low, which causes a problem in tackiness after precure (drying of the coating film), which makes contact exposure impossible and causes contamination of the mask.

Next, the compound (B) having an epoxy group
(Hereinafter, referred to as B component) includes phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin,
Epoxy resin such as biphenyl type epoxy resin and alicyclic epoxy resin, and at least one epoxy group such as phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether and glycidyl methacrylate. And the like.

Further, a photopolymerization initiator or a sensitizer (C) constituting the resin composition of the present invention (hereinafter referred to as C component)
Is used not only as the A component but also as a photopolymerization initiator for a monomer or an oligomer that can be polymerized by light, which is compounded as necessary. As the C component used for such a purpose, , For example, acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, benzophenone, and 2-chlorobenzophenone. , P, p′-bisdimethylaminobenzophenone and other benzophenones, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether,
Benzoin ethers such as benzoin isobutyl ether, benzyl dimethyl ketal, thioxanthone,
Sulfur compounds such as 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, Anthraquinones such as 2,3-diphenylanthraquinone, organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, etc. And the thiol compound. These compounds can also be used in combination of two or more kinds. Further, a compound which does not act as a photopolymerization initiator by itself but which can increase the ability of the photopolymerization initiator by using it in combination with the above compound can be added. Examples of such compounds include tertiary amines such as triethanolamine, which are effective when used in combination with benzophenone.

The photosensitive resin composition of the present invention comprises the components A, B
The resin composition is composed of component C and component C, and the blending ratio of each component in this resin composition is 5 to 50 parts by weight and 0.1 to 30 parts by weight with respect to 100 parts by weight of component A, respectively. Among these, a composition in which the proportions of the B component and the C component are 10 to 30 parts by weight and 1 to 20 parts by weight, respectively, relative to 100 parts by weight of the A component is particularly preferable. When the blending ratio of the component B is less than 5 parts by weight relative to 100 parts by weight of the component A, the properties of the composition of the present invention after curing, particularly alkali resistance are insufficient, and when it exceeds 100 parts by weight, the curing is difficult. Occasionally, cracks occur, and the adhesion tends to decrease. A component 100
When the mixing ratio of the C component to the weight part is less than 0.1 part by weight, the photopolymerization rate becomes slow and the sensitivity is lowered. On the other hand, when the amount exceeds 30 parts by weight, it is difficult for light to reach the substrate, and the adhesion between the substrate and the resin deteriorates.

The photosensitive resin composition of the present invention can be suitably used as a color filter protective film for a color liquid crystal display. ITO can be sputtered onto this protective film at a high temperature of 250 ° C. (the maximum temperature is 200 ° C. because the conventional protective film does not have heat resistance).
It can withstand strong acid and strong alkali treatment during patterning.

Examples of the developing solution suitable for alkali developing the resin composition of the present invention include an aqueous solution of an alkali metal or alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like. It is possible, but especially 1 to 3 of carbonates such as sodium carbonate, potassium carbonate and lithium carbonate.
Fine images can be precisely developed even by using a weakly alkaline aqueous solution containing 1% by weight. The alkali development of the resin composition of the present invention is 10 to 50 ° C., preferably 20 to 4
It can be carried out at a temperature of 0 ° C. using a commercially available developing machine or ultrasonic cleaning machine.

The photosensitive resin composition of the present invention can be cured not only by light but also by heat. Suitable for curing by light is an ultrahigh pressure mercury lamp, a high pressure mercury lamp or a metal halide lamp. The light emitted from the lamp is mentioned.

When the photosensitive resin composition of the present invention is used as a solder resist for a printed wiring board in addition to the protective film for the color filter of the color liquid crystal display as described above, first, the surface of the printed wiring board is used. To form a solution by applying the resin composition of the present invention to the solution, or by applying a dry film comprising the resin composition of the present invention to the surface of the printed wiring board to form a coating film, then, A negative film is placed on the obtained coating, and the exposed areas are cured by irradiation with actinic rays, and the unexposed areas are eluted with a weak alkaline aqueous solution.

After the alkali development, in order to improve the alkali resistance, it is desirable to heat it to perform an epoxy curing treatment. In the resin composition of the present invention, by performing heat treatment, not only the durability to strong alkaline water is significantly improved, but also glass, adhesion to metals such as copper, heat resistance, and solder resist such as surface hardness. The required properties are also improved. The heating temperature and the heating time under the heat curing conditions are, for example, 80 to 20 respectively.
0 degreeC and 10 to 120 minutes are mentioned.

Examples of the solvent suitable for preparing the solution of the resin composition in the present invention include ketones such as methyl ethyl ketone and methyl isobutyl ketone, and cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and cellosolve acetate. Be done.

As the method for applying the solution of the resin composition in the present invention to the substrate, in addition to the solution dipping method, the spray method,
Any method such as using a roller coater machine or a spinner machine can be adopted. By these methods, a film is formed by applying the resin composition solution to a thickness of 1 to 30 microns and then removing the solvent.

In the resin composition of the present invention, in addition to the above-mentioned component A, a monomer or an oligomer which can be polymerized by light can be blended in accordance with the physical properties of its intended use. Examples of such light-polymerizable monomers and oligomers include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, and ethylene. Glycol di (meta)
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, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, etc. (Meth) acrylic acid esters of These compounds are
Only one species may be used alone, or two or more species may be used in combination. Then, such a monomer or oligomer acts as a viscosity modifier or a photocrosslinking agent, and the amount thereof 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 further added in an amount of 50 parts by weight or less based on 100 parts by weight of the photopolymerizable unsaturated compound represented by the general formula (1). If the amount of the monomer or oligomer used exceeds 50 parts by weight, the tackiness after pre-curing will be a problem.

If necessary, additives such as an epoxy group curing accelerator, a thermal polymerization inhibitor, a plasticizer, a leveling agent and a defoaming agent can be added to the above-mentioned photosensitive resin composition. Examples of the epoxy group curing accelerator include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, and methylol group-containing compounds, and the like. It is possible to improve various properties such as heat resistance, solvent resistance, acid resistance, plating resistance, adhesiveness, electric characteristics and hardness of the obtained resist film. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like. Further, as the plasticizer, dibutyl phthalate, dioctyl phthalate,
Examples include tricresyl. Examples of the defoaming agent and the leveling agent include silicon-based, fluorine-based, and acrylic compounds.

Next, an example of the method for producing a film by photopolymerization of the photosensitive resin of the present invention and the composition thereof will be described. First, the photosensitive resin composition of the present invention is diluted with a solvent, and additives such as a suitable photoinitiator, photoinitiator aid, coupling agent, and antioxidant are added to prepare a resist solution. Next, the resist solution is coated on the substrate by an arbitrary method. Although spin coating is used in the embodiments, coating methods such as dip coating and bar coating are of course possible. After coating the resist solution, precure is performed to evaporate the solvent. Next, contact exposure is performed using an ultra-high pressure mercury lamp, and the unexposed area is developed with a 1% sodium carbonate aqueous solution and further washed with water. And 200
Completely dry the coating by post-curing at ℃,
It is possible to obtain a desired coating film having excellent heat resistance, transparency, adhesion, hardness, solvent resistance, alkali resistance and the like.

[0026]

EXAMPLES The present invention will be specifically described below based on synthesis examples, examples and comparative examples. In addition, about the photopolymerizable unsaturated compound of this invention, it shows as Synthesis Examples 1-12. In addition, in the following synthesis examples, examples and comparative examples, "part" means "part by weight".

Synthesis Example 1 In a 500 ml four-necked flask, 231 g of bisphenolfluorene type epoxy resin (epoxy equivalent 231) and 450 m of triethylbenzylammonium chloride were added.
g, 2,6-diisobutylphenol (100 mg) and acrylic acid (72.0 g) were charged, and the mixture was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, gradually raise the temperature of the solution in a cloudy state,
It was heated to 120 ° C. and completely dissolved. Here, the solution gradually became transparent and viscous, but the stirring was continued as it was. During this period, the acid value was measured, and heating and stirring were continued until the acid value was less than 2.0 mgKOH / g. It took 8 hours for the acid value to reach the target (acid value: 0.8). Then, the mixture was cooled to room temperature to obtain a colorless and transparent bisphenolfluorene type epoxy acrylate represented by the general formula (4).

Then, 303 g of the above-mentioned bisphenol fluorene type epoxy acrylate thus obtained
After adding 2 kg of cellosolve acetate to dissolve it,
38 g of 1,2,3,6-tetrahydrophthalic anhydride, 80.5 g of benzophenone tetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually heated to react at 110 to 115 ° C. for 2 hours, A compound 1 of the general formula (1) (m / n = 5/5 in the formula) was obtained. The reaction of the acid anhydride was confirmed by IR spectrum. Also,
The obtained compound had an inherent viscosity of 0.3 dl / g
(Η _inh = 0.3).

Synthesis Example 2 Using 303 g of the bisphenolfluorene type epoxy acrylate of the general formula (4) produced in Synthesis Example 1, 2 kg of cellosolve acetate was added to form a solution,
121.6 g of 3,6-tetrahydrophthalic anhydride, 64.6 g of benzophenone tetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually heated to react at 110 to 115 ° C. for 2 hours. (1)
Compound 2 (m / n = 8/2 in the formula) was obtained. The reaction of the acid anhydride was confirmed by IR spectrum as in Synthesis Example 1 above. The inherent viscosity of the obtained compound was 0.2 dl / g (η _inh = 0.2). IR spectra before and after the reaction are shown in FIG. 1 (before the reaction) and FIG. 2 (after the reaction), respectively.

Synthesis Example 3 Using 303 g of the bisphenolfluorene type epoxy acrylate of the general formula (4) prepared in Synthesis Example 1, 2 kg of cellosolve acetate was added to form a solution, and then 1, 2,
3.8 g of 3,6-tetrahydrophthalic anhydride, 153.8 g of benzophenone tetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were mixed, and the temperature was gradually raised to react at 110 to 115 ° C. for 2 hours. A compound 3 of (1) (m / n in the formula = 0.5 / 95.5) was obtained.
The reaction of the acid anhydride was confirmed by IR spectrum. The inherent viscosity of the obtained compound is 0.3 dl /
It was g (η _inh = 0.3).

Synthesis Example 4 303 g of the bisphenol fluorene type epoxy acrylate resin produced in Synthesis Example 1 was added to 2 kg of cellosolve acetate to form a solution, and then 72.2 g of 1,2,3,6-tetrahydrophthalic anhydride and benzophenone were used. 8.05 g of tetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually heated to 110
The compound 4 of the general formula (1) is reacted at 115 ° C. for 2 hours.
(M / n of Formula 1 = 95/5) was obtained. The reaction of the acid anhydride was confirmed by IR spectrum. The inherent viscosity of the obtained compound was 0.2 dl / g (η _inh = 0.
It was 2).

Synthesis Example 5 A compound was obtained by reacting with an acid anhydride in the same manner as in Synthesis Example 1 except that 153 g of biphenyl type epoxy resin (epoxy equivalent 153) was used in place of the bisphenol fluorene type epoxy resin in Synthesis Example 1. 5 [m in the general formula (1)
/ N = 5/5) was obtained. At this time, the reaction with the acid anhydride is I
Confirmed by R spectrum. The obtained compound 5 had an inherent viscosity of 0.2 dl / g (η _inh = 0.2).

Synthesis Example 6 Instead of the bisphenolfluorene type epoxy resin in Synthesis Example 1, 163 g of benzophenone type epoxy resin
Compound 6 [general formula (1) was reacted with an acid anhydride in the same manner as in Synthesis Example 1 except that (epoxy equivalent 163) was used.
M / n = 5/5) was obtained. The reaction with the acid anhydride at this time was confirmed by IR spectrum. The obtained compound 6 had an inherent viscosity of 0.3 dl / g (η _inh = 0.3)
Met.

Synthesis Example 7 A compound was obtained by reacting with an acid anhydride in the same manner as in Synthesis Example 1 except that 181 g of a sulfone type epoxy resin (epoxy equivalent 181) was used in place of the bisphenol fluorene type epoxy resin in Synthesis Example 1. 7 [m / in the general formula (1)
n = 5/5) was obtained. The reaction with the acid anhydride at this time is IR
Confirmed by spectrum. The obtained compound 7 had an inherent viscosity of 0.3 dl / g (η _inh = 0.3).

Synthesis Example 8 Reaction with an acid anhydride was carried out in the same manner as in Synthesis Example 1 except that 221 g of hexafluoropropane type epoxy resin (epoxy equivalent 221) was used in place of the bisphenol fluorene type epoxy resin in Synthesis Example 1. , Compound 8 [m / n of general formula (1) = 5/5] was obtained. The reaction with the acid anhydride at this time was confirmed by IR spectrum. The obtained compound 8 had an inherent viscosity of 0.4 dl / g (η _inh =
0.4).

Synthesis Example 9 In place of the bisphenol fluorene type epoxy resin used in Synthesis Example 1, 163 g of dimethylsilane type epoxy resin.
Compound 9 [general formula (1) was reacted with an acid anhydride in the same manner as in Synthesis Example 1 except that (epoxy equivalent 163) was used.
M / n = 5/5) was obtained. The reaction with the acid anhydride at this time was confirmed by IR spectrum. The obtained compound 9 had an inherent viscosity of 0.2 dl / g (η _inh = 0.2)
Met.

Synthetic Example 10 Instead of the bisphenol fluorene type epoxy resin in Synthetic Example 1, biphenylmethane type epoxy resin 156.
Compound 10 [m / n of general formula (1) = 5/5] was obtained by reacting with an acid anhydride in the same manner as in Synthesis Example 1 except that g (epoxy equivalent of 156) was used. The reaction with the acid anhydride at this time was confirmed by IR spectrum. The obtained compound 10 had an inherent viscosity of 0.4 dl / g (η _inh =
0.4).

Synthesis Example 11 Biphenylpropane type epoxy resin 17 was used in place of the bisphenolfluorene type epoxy resin in Synthesis Example 1.
Synthesis Example 1 except that 0 g (epoxy equivalent 170) was used
It was reacted with an acid anhydride in the same manner as in, to obtain Compound 11 [m / n of general formula (1) = 5/5]. The reaction with the acid anhydride at this time was confirmed by IR spectrum. The obtained compound 11 had an inherent viscosity of 0.4 dl / g (η _inh =
0.4).

Synthetic Example 12 Instead of the bisphenol fluorene type epoxy resin in Synthetic Example 1, a biphenyl ether type epoxy resin 15 was used.
Synthesis Example 1 except that 7 g (epoxy equivalent 157) was used
Compound 12 [m / n of general formula (1) = 5/5] was obtained by reacting with an acid anhydride in the same manner as in. The reaction with the acid anhydride at this time was confirmed by IR spectrum. The obtained compound 12 had an inherent viscosity of 0.3 dl / g (η _inh =
It was 0.3).

Examples 1 to 14 and Comparative Examples 1 to 3 Component A obtained in the above Synthesis Examples 1 to 12, component B, component C, a photopolymerizable acrylic monomer or oligomer and an organic solvent were blended in the following proportions. Then, the resist solutions of Examples 1 to 14 and Comparative Examples 1 to 3 were prepared.

Example 1 (m / n = 5/5) Ratio (parts by weight) Compound 1 20 Tetramethylbiphenyl type epoxy resin 3 Michler's ketone 0.1 Irgacure 907 (manufactured by Ciba Geigy) 0.6 Cellosolve acetate 76.3 Total 100

Example 2 (m / n = 5/5) Ratio (parts by weight) Compound 1 20 Dipentaerythritol hexaacrylate 8.6 Tetramethylbiphenyl type epoxy resin 4.4 Michler's ketone 0.2 Irgacure 907 (Ciba Geigy) 1.2) Cellosolve acetate 65.6 Total 100

Example 3 (m / n = 8/2) Ratio (parts by weight) Compound 2 20 Tetramethylbiphenyl type epoxy resin 3 Michler's ketone 0.1 Irgacure 907 (manufactured by Ciba-Geigy) 0.6 Cellosolve acetate 76.3 Total 100

Example 4 (m / n = 8/2) Ratio (parts by weight) Compound 2 20 Dipentaerythritol hexaacrylate 8.6 Tetramethylbiphenyl type epoxy resin 4.4 Michler's ketone 0.2 Irgacure 907 (Ciba Geigy) 1.2) Cellosolve acetate 65.6 Total 100

Example 5 (m / n = 5/5) Ratio (parts by weight) Compound 1 20 Tetramethylbiphenyl type epoxy resin 3 Michler's ketone 0.1 Irgacure 907 (manufactured by Ciba Geigy) 0.6 Cellosolve acetate 76.3 Total 100

Example 6 (m / n = 5/5) Ratio (parts by weight) Compound 1 20 Dipentaerythritol hexaacrylate 8.6 Tetramethylbiphenyl type epoxy resin 4.4 Michler's ketone 0.2 Irgacure 907 (Ciba Geigy) 1.2) Cellosolve acetate 65.6 Total 100

Example 7 (m / n = 5/5) Ratio (parts by weight) Compound 5 20 Tetramethylbiphenyl type epoxy resin 3 Michler's ketone 0.1 Irgacure 907 (manufactured by Ciba Geigy) 0.6 Cellosolve acetate 76.3 Total 100

Example 8 (m / n = 5/5) Ratio (parts by weight) Compound 6 20 Tetramethylbiphenyl type epoxy resin 3 Michler's ketone 0.1 Irgacure 907 (manufactured by Ciba Geigy) 0.6 Cellosolve acetate 76.3 Total 100

Example 9 (m / n = 5/5) Ratio (parts by weight) Compound 7 20 Tetramethylbiphenyl type epoxy resin 3 Michler's ketone 0.1 Irgacure 907 (manufactured by Ciba-Geigy) 0.6 Cellosolve acetate 76.3 Total 100

Example 10 (m / n = 5/5) Ratio (parts by weight) Compound 8 20 Tetramethylbiphenyl type epoxy resin 3 Michler's ketone 0.1 Irgacure 907 (manufactured by Ciba Geigy) 0.6 Cellosolve acetate 76.3 Total 100

Example 11 (m / n = 5/5) Ratio (parts by weight) Compound 9 20 Tetramethylbiphenyl type epoxy resin 3 Michler's ketone 0.1 Irgacure 907 (manufactured by Ciba Geigy) 0.6 Cellosolve acetate 76.3 Total 100

Example 12 (m / n = 5/5) Ratio (parts by weight) Compound 10 20 Tetramethylbiphenyl type epoxy resin 3 Michler's ketone 0.1 Irgacure 907 (manufactured by Ciba Geigy) 0.6 Cellosolve acetate 76.3 Total 100

Example 13 (m / n = 5/5) Ratio (parts by weight) Compound 11 20 Tetramethylbiphenyl type epoxy resin 3 Michler's ketone 0.1 Irgacure 907 (manufactured by Ciba-Geigy) 0.6 Cellosolve acetate 76.3 Total 100

Example 14 (m / n = 5/5) Ratio (parts by weight) Compound 12 20 Tetramethylbiphenyl type epoxy resin 3 Michler's ketone 0.1 Irgacure 907 (manufactured by Ciba Geigy) 0.6 Cellosolve acetate 76.3 Total 100

Comparative Example 1 (m / n = 0.5 / 95.5) Ratio (parts by weight) Compound 3 20 Tetramethylbiphenyl type epoxy resin 3 Michler's ketone 0.1 Irgacure 907 (manufactured by Ciba Geigy) 0.6 Cellosolve Acetate 76.3 Total 100

Comparative Example 2 (m / n = 95/5) Ratio (parts by weight) Compound 4 20 Dipentaerythritol hexaacrylate 8.6 Tetramethylbiphenyl type epoxy resin 4.4 Michler's ketone 0.2 Irgacure 907 (Ciba Geigy) 1.2) Cellosolve acetate 65.6 Total 100

Comparative Example 3 (m / n = 5/5) Ratio (parts by weight) Compound 1 20 Dipentaerythritol hexaacrylate 12 Tetramethylbiphenyl type epoxy resin 4.8 Michler's ketone 0.2 Irgacure 907 (manufactured by Ciba Geigy) 1.2 Cellosolve acetate 61.8 Total 100

Then, these resist solutions were applied to a degreased and washed glass plate having a thickness of 1.2 mm to a thickness of about 2 μm and dried, and then a photomask was brought into close contact with the glass plate, and 500
Illuminance 10 at a wavelength of 365 nm using a high-pressure mercury lamp of W
Ultraviolet light of mw / cm ² was irradiated for 20 seconds. After exposure, 1
Development was carried out at 25 ° C. for 30 seconds with a weight% sodium carbonate aqueous solution to remove the unexposed portion of the coating film. After that, heat drying treatment was performed at 200 ° C. for 30 minutes using a hot air dryer.

With respect to the obtained samples, the drying property of the coating film, the developability with respect to an alkaline aqueous solution, the exposure sensitivity, the coating film hardness, the adhesion to the substrate, the heat resistance and the chemical resistance were evaluated. The results are shown in Table 1. Various physical property data were measured under the following conditions.

(1) Drying property of coating film The drying property of the coating film was evaluated according to JIS-K5400. The evaluation ranks are as follows. ◯: No tack is observed at all Δ: Slight tack is observed x: Remarkably tack is observed

(2) Developability in Alkaline Aqueous Solution Development was carried out by immersing in a 1 wt% sodium carbonate aqueous solution for 30 seconds. After the development, the resin was enlarged 40 times and the remaining resin was visually evaluated. The evaluation ranks are as follows. ◯: Good developability (no resist left on the glass) X: Poor developability (some resist left on the glass)

(3) Exposure sensitivity Kodak step tablet No. 2 (manufactured by Eastman Kodak Company, negative film having optical density steps of 0.15 and 21 steps) was adhered to the coating film, and a light amount of 200 mj / cm ² was irradiated using a 500 W high-pressure mercury lamp. Next, this coating film was examined for the number of steps of the step tablet for the weak alkaline aqueous solution described above (in this evaluation method, the higher the sensitivity, the greater the number of remaining steps).

(4) Hardness of coating film After the exposure and development, the hardness of the coating film heated at 200 ° C. for 30 minutes was measured by applying a load of 1 kg using a pencil hardness tester according to the test method of JIS-K5400. The highest hardness that does not scratch the coating film was displayed. The pencil used is "Mitsubishi High Uni."

(5) Adhesion with Substrate After exposure and development, a coating film heated at 200 ° C. for 30 minutes was used.
A cross cut was inserted so as to make at least 100 grids, and then a peeling test was performed using cellophane tape, and the state of peeling of the grids was visually evaluated. The evaluation ranks are as follows. ◯: No peeling was observed at all x: Peeling was observed even a little (6) Heat resistance After exposure and development, a coating film heated at 200 ° C. for 30 minutes was 2
The state of the coating film was evaluated by placing it in an oven at 50 ° C. for 3 hours.
The evaluation ranks are as follows. ◯: There is no abnormality in the appearance of the coating film. X: There is peeling or coloring in the appearance of the coating film.

(7) Chemical resistance After exposure and development, a coating film heated at 200 ° C. for 30 minutes was
It was immersed in the following chemicals under the following conditions, and the appearance and adhesion after immersion were evaluated. Acid resistance 24 hours in 5% HCl Alkali resistance Soaking in 5% NaOH for 24 hours 4% KOH at 50 ° C for 10 minutes 1% NaOH at 80 ° C for 5 minutes Solvent resistance NMP at 40 ° C for 10 minutes NMP at 80 ° C 5 minutes (Note) NMP: N-methyl-pyrrolidone

[0066]

[Table 1]

As is clear from the results shown in Table 1, Examples 1 to 14 could achieve the desired physical properties. However, as in Comparative Example 1, at a molar ratio of m / n = 0.5 / 95.5, the amount of carboxyl groups in the photopolymerizable unsaturated compound was large, and the cured part also dissolved in the alkaline aqueous solution during development. I can't get what I want. Further, as in Comparative Example 2, m / n = 95
At a molar ratio of / 5, contrary to Comparative Example 1, the amount of carboxyl groups in the photopolymerizable unsaturated compound is small and the developability with an aqueous alkali solution is poor. Further, in Comparative Example 3, the amount of the photopolymerizable acrylic oligomer (dipentaerythritol hexaacrylate) blended was large, the tackiness remained in the coating film after precuring, and contact exposure was difficult. From the above results, it was revealed that the photosensitive resin composition of the present invention can provide a protective film having excellent heat resistance, transparency, adhesion, hardness, solvent resistance, alkali resistance and the like.

[0068]

INDUSTRIAL APPLICABILITY The photopolymerizable unsaturated compound of the present invention and the photosensitive resin composition using the same are alkali-developable photosensitive resin compositions excellent in heat resistance and transparency, which cannot be achieved by conventional ones. Is. Therefore, the resin composition of the present invention is advantageous in that the coating film becomes tack-free after precure, contact exposure becomes possible, and resolution is improved. Moreover, since the photopolymerizable unsaturated compound of the present invention and the photosensitive resin composition using the same are excellent in acid resistance, alkali resistance, solvent resistance, surface hardness, etc., they are permanent protection masks such as solder resists. It is not only useful for various purposes such as printed wiring board-related etching resists, interlayer insulation materials, photosensitive adhesives, paints, photosensitive liquids for screen printing and resist inks, but also for photosensitive resins and resin compositions. It can be used as a thing.

[Brief description of drawings]

FIG. 1 is a graph showing an IR spectrum before a reaction in Synthesis Example 2.

FIG. 2 is a graph showing an IR spectrum after the reaction in Synthesis Example 2.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location G03F 7/038 501 H05K 3/28 D 7511-4E // C08G 59/17 NHG 8416-4J

Claims (6)

[Claims] 1. The following general formula (1): (However, in the formula, R ₁ and R ₂ are any of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a halogen atom,
R ₃ is a hydrogen atom or a methyl group, X is —CO—, —
_{SO 2 -, - C (CF} 3) 2 -, - Si (CH 3)
_{2 -, - CH 2, -C} (CH 3) 2 -, - O- or ## STR2 ## Or absent, Y represents a residue of an acid anhydride, Z
Represents a residue of an acid dianhydride, m: n of the number of structural units is represented by a molar ratio of 1/99 to 90/10), and 0.5 g of the compound is represented by N-methyl. Pyrrolidone 10
A photopolymerizable unsaturated compound having an inherent viscosity (η _inh ) of 0.1 dl / g or more measured at 30 ° C. in a solution dissolved in 0 ml. 2. X in the general formula (1) is The photopolymerizable unsaturated compound according to claim 1, which is 3. A photopolymerizable unsaturated compound represented by the general formula (1), (B) an epoxy group-containing compound, and (C) a photopolymerization initiator or a sensitizer. , Above A
An alkali-developable photosensitive resin composition, characterized in that the proportions of the above-mentioned component B and component C relative to 100 parts by weight of the component are 5 to 50 parts by weight and 0.1 to 30 parts by weight, respectively. 4. The alkali-developable photosensitive resin composition according to claim 3, wherein R _{1 to} R ₃ in the general formula (1) are hydrogen atoms. 5. X in the general formula (1) is The alkali-developable photosensitive resin composition according to claim 3. 6. A photopolymerizable unsaturated compound 1 of the general formula (1)
5 parts by weight of at least one of a (meth) acrylic monomer and a (meth) acrylic oligomer with respect to 100 parts by weight
The alkali-developable photosensitive resin composition according to any one of claims 3 to 5, which is blended in an amount of 0 part by weight or less.