JPS60121444A - Alkali-developable photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain an intended resin compsn. capable of hardening a thick film, high in sensitivity and resolution, and good in durability by forming a compsn. consisting of a specified chain polymer, an epoxy compd., a photopolymerizable compd., a compd. having a functional group reactive with said three compds, a sensitizer, etc. CONSTITUTION:An intended photosensitive resin compsn. consists of (a) a chain polymer having groups reactive with epoxy and hydroxyl groups on both terminals of the molecule and a number average mol.wt. of 500-20,000, (b) a aliphatic or alicyclic multifunctional epoxy compd., (c) a compd. having a photopolymerizable double bond and capable of reacting with the functional groups of the reaction product mixture of both (a) and (b), (d) a compd. having acid anhydride groups or a compd. having functional groups reactive with the functional groups of the reaction product mixture of (a), (b), and (c), and (e) a sensitizer. The component (a) has any of COOH, NH2, SH, NCO, and OH on both terminals, and 1-5mol of the component (b) is reacted with 1 equiv. of the epoxy group of the component (a) or its functional group reactive with OH; 0.2-1.0mol of the component (c) is reacted with 1 equiv. of the epoxy group of the reaction product mixture of (a) and (b), and 0.2-1.0mol of the component (d) is reacted with 1 equiv. of the functional group of epoxy acrylate obtained by this reaction to obtain an intended photosensitive compsn.

Description

[Detailed description of the invention] The present invention relates to an alkali-developable photosensitive resin composition.

More specifically, the present invention relates to an alkali-developable photosensitive resin composition that can be cured into a thick film and has high resolution and excellent durability.

Conventionally, alkaline-developable photosensitive resins have been developed as liquid photoresists such as polyvinyl alcohol-based, polybutadiene-based, aromatic diazo compound-based resins made of phenolic resins, and novolac resins, and have been developed as alkali-developable dry films and are not commercially available. It has been tested.

Examples of polyvinyl alcohol-based photosensitive resins include J, Appl, Polymer Sci, + Vol.
, 2+P-302 ('59) is an alkali-developable liquid photoresist that uses polyvinyl alcohol as a backbone polymer and has carboxyl groups and cinnamic acid introduced into the side chains and uses a dilute alkaline aqueous solution as a developer. Yes, those described in Special Publication No. 49-5923 are:
This is a water-developable liquid photoresist made by reacting polyvinyl alcohol with N-methylol acrylamide, and the one described in JP-A-49-4738 is esterified with succinic anhydride and further treated with diglycidyl methacrylate. Alkaline-developable liquid photoresists with added oxides are known. Although these alkali-developable photoresists have excellent developability, the photocured film has
Various properties such as acid resistance, alkali resistance, and water resistance are not sufficient, and the photosensitive properties are not necessarily satisfactory. Therefore, the alkali-developable polyvinyl alcohol-based liquid photoresist has the disadvantage of being a thin film and lacking in durability.

As a polybutadiene-based photosensitive resin, for example, the one described in Japanese Patent Publication No. 54-15789 consists of a resin skeleton in which a mercapto compound is added to a polybutadiene polymer and a photosensitive group is further introduced. This has improved the dark reaction, resolution, acid resistance, alkali resistance, etc. of polyvinyl photosensitive resins, but when forming images, organic solvents are mainly used as developing solutions, and diluted alkaline aqueous solutions are sufficient. It cannot be developed and requires further improvement, and although the tack-free properties of the film surface when photosensitive resin is applied to the substrate have been improved, the tackiness of the formed film has been completely removed. However, the thick film curing was also not satisfactory.

As photosensitive resins based on aromatic diazo compounds such as phenolic resins and novolak resins, for example,
The photoresist described in No. 15664 is a reaction product of an aromatic diazonicium salt and a water-soluble sulfonated phenol resin, and is a positive photoresist that is soluble in an alkaline aqueous solution.

Also, US Patent No. 3046120, German Patent No. 865
What is described in No. 860 is an alkali-developable positive photoresist made of a condensate of a polymerized O-naphthoquinone diazide compound and a novolak resin. These photosensitive resin compositions have hydroxyl groups, amine groups, etc., such as novolak, polyaminostyrene, and phenolic resins.They are synthesized by a polymer reaction of one polymer, but since they are positive photoresists, they have poor weather resistance. It has been difficult to provide photoresists with high sensitivity and excellent durability.

For example, the alkaline developing type dry film is
-25231, and is a very reliable product with a thick film and no worries about pinholes. but,
Because it is processed using a special laminator, the work is very complicated, it lacks adhesion to the substrate, and it is not durable. Furthermore, because of the thick film, it lacks resolution, is difficult to process into fine patterns, and is expensive.

Therefore, the alkali-developable photosensitive resins on the market form images in thin films and are mainly put into practical use as temporary casts for etching. Although it has the performance as a temporary resist because it peels off, it has the durability of the coating film such as soldering heat resistance, chemical resistance, solvent resistance, moisture resistance, and water resistance. 6- What is the resin composition? is not.

In fact, alkaline-developable photosensitive resins focused on etching resistance, photosensitive characteristics, and peelability, but did not consider the durability of the coating film, nor did they consider use in thick films. .

The purpose of the present invention is to improve the drawbacks of the above-mentioned known techniques, to enable thick film curing, and to have excellent sensitivity, resolution, and film durability.
Another object of the present invention is to provide a photosensitive resin composition that has alkaline developability and tack-free longevity.

As a result of extensive studies, the present inventors have found that the intended purpose of the present invention can be achieved by using the photosensitive resin composition obtained by the present invention, and have completed the present invention.

That is, the present invention provides a photosensitive resin obtained by reacting (a) (a) with a functional group that reacts with an epoxy group or a hydroxyl group at both ends of the molecule. (b) one or more epoxy compounds selected from polyfunctional epoxy compounds having an aromatic ring and alicyclic polyfunctional epoxy compounds; c) It has at least one double bond that can be polymerized by irradiation with actinic rays, and has a functional group that can react with the functional group present in the reaction mixture of (a) and 6) above. (d) A compound having one or more acid anhydride groups or one or more carboxyl groups or phenolic hydroxyl groups, and obtained by reacting the above (a), (b) and (c). a compound having one or more functional groups capable of reacting with a functional group present in the reaction mixture; This is an alkali-developable photosensitive resin composition characterized by comprising a sensitizer, the above-mentioned (A) and (B) as main components.

Next, the present invention will be explained in detail.

Photosensitive resin (5), which is one of the main components of the alkali-developable photosensitive resin composition used in the present invention, is synthesized as follows.

First, the number average molecular weight is 500 to 500, which has a functional group that reacts with the epoxy group or hydroxyl group, which is component (a), at both ends of the molecule.
The chain of 2QOOO is extended by polymeric reaction between the chain polymer compound and the polyfunctional epoxy resin which is a component of 2QOOO. Next, component (c) has a double bond that can be polymerized by actinic ray irradiation and has a functional group that can react with the functional group remaining in the reaction mixture of components (a) and (b). The compounds are reacted to introduce polymerizable double bonds.

Next, a reaction obtained by reacting a compound having an acid anhydride group or one or more carboxyl groups or a phenolic hydroxyl group, which is component (d), and components (a), (b), and (c). A photosensitive resin matrix is obtained by reacting a compound having one or more functional groups capable of reacting with the functional groups remaining in the mixture to introduce a functional group soluble in an alkaline aqueous solution.

9- (R) n/// (Z)go' -(Y)-(Z)m” ・・・・・・・・・
・It is shown in a general formula like [2] formula, and [1] formula or [
It is a mixture of formulas [1] and [2].

However, here, X: a chain polymer compound (a
), one or more epoxy compounds (b) selected from polyfunctional epoxy compounds having an aromatic ring, and alicyclic polyfunctional epoxy compounds (b); a)
and an organic residue of a polyfunctional epoxy compound reacted with a compound (c) having at least one double bond that can be polymerized by irradiation with actinic rays; Compounds having at least one or more heavy bonds (c
) an organic residue reacted with the polyfunctional epoxy compound (b),
R: one functional group capable of reacting with a functional group present in the reaction mixture obtained by reacting a compound having an acid anhydride group or one or more carboxyl groups or phenolic hydroxyl groups and (C) Compound (d) with
The organic residues that reacted with the chain polymer compound (a) or the polyfunctional epoxy compound, m1, residue', d''; integer from 1 to 8, n, n', n//, n/ l/: integer from 1 to 8, p, p'
: Indicates an integer from O to 3.

The general formula of the photosensitive resin compound (6) shown above is a typical general formula, and is not limited to these. b),
Any photosensitive resin compound (6) obtained by reacting (c) and (d) may be used.

The chain polymer compound (a) used in the present invention is a compound with a number average molecular weight of 500 to 20,000 selected from the group having carboxyl groups, amine groups, thiol groups, incyanate groups, hydroxyl groups, etc. at both ends of the molecule. For example, as a resin type, poly(meth)acrylic type, polydiene type, polystyrene type, polyvinyl chloride type, polyvinylidene chloride M1. l-"!J Vinyl acetate type, polyvinyl formal type, polyvinyl acetal type, polyvinyl butyral type, polyvinyl alcohol type, polyvinylpyrrolidone type, polyurethane type, polyether type, polyamide type, ketone resin type, silicone resin type, sulfonamide formaldehyde Examples of these resin systems include polymers such as those of the present invention, and copolymers thereof.Among these resin systems, particularly those that have the characteristics of the present invention, such as thick film curing sensitivity, resolution,
Polydiene chain polymer compounds are particularly desirable in order to offer photosensitive resins with excellent film durability, alkali developability, workability, etc. As a specific example of the polydiene-based chain polymer compound, Nippon Soda ■ trade name: Nl5SO-PBG-100
0, Nl5SO-PBG -2000, Nl5SO-PBG -3000, Nl5SO-PBC-1000, Nl5SO-PBG -2000, Arco product name: poly BD -R-45M
.

poly BD-R-45HT.

poly BD-C8-15, poly BD-CN-15, Philips product name: ButarezCTL.

Butarez HT.

Gutdrich product name: Hycar-CTB, H
ycar-CTBN.

Hycar-CTBN.

Hycar-HTB.

General Tire Company's product name: TelogenCT.

TelogenHT etc. can be mentioned.

In addition, by using these polydiene-based chain polymer compounds as the main component in combination with the resin system which is the chain polymer compound described above, the photosensitive properties, coating film performance, tack-free properties, etc. of the photosensitive resin (6) can be improved. It is also possible to improve the web properties. On the other hand, the number average molecular weight of the chain polymer compound is between 500 and 2QOOO, and if it is less than 500, it has the disadvantage that tack-free properties are difficult due to the low molecular weight and stickiness remains during preheating.13-20. If it is larger than 000, the viscosity increases significantly during the reaction, resulting in poor workability and is likely to gel. Therefore, since it depends on workability, various performances, etc., the number average molecular weight is
It is desirable to use one with a diameter of 5ooo.

Polyfunctional epoxy compound having an aromatic ring and alicyclic polyfunctional epoxy compound (b) used in the present invention
Examples include the diglycidyl ether type of bisphenol A, the diglycidyl type of hydrogenated bisphenol A, the diglycidyl ether type of bisphenol F, the diglycidyl ether type of hydrogenated bisphenol F, the novolac type, and the tetrahydroxyphenylethane type. Examples include epoxy resins such as glycidyl ether type, alicyclic type, and polydiene-modified epoxy compounds.

In addition, various aliphatic epoxy resins such as polyglycol diglycidyl ether type, polyolefin type, dimer acid-modified epoxy compounds, epoxidized soybean oil, etc. or various modified epoxy resins may be used within a range that does not impede the tack-free properties of the photosensitive resin composition. It can be used in combination with resin.

Tack-free 14- Considering the properties, gelation during reaction, and physical properties of the photosensitive resin composition, it is a bisphenol type, novolac type, or alicyclic type di- or trifunctional epoxy compound with a number average molecular weight. Compounds with a molecular weight of 500 to 2QOOO are preferred. The above epoxy compounds can be used alone or in combination of two or more.

It has at least one double bond that can be multipolymerized by irradiation with actinic rays used in the present invention, and is capable of reacting with the functional group present in the reaction mixture of (a) and (b) described above. The compound (c) having one or more functional groups includes a (meth)acryloyl group, an allyl group, an ihahinyl group, etc., and any functional group such as a carboxyl group, a hydroxyl group, an amine group or an incyanate group. It is a compound that has

For example, (meth)acrylic acids such as acrylic acid and methacrylic acid; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyisopropyl (meth)acrylate, diethylene glycol (meth)acrylate, Triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, triprobylene glycol di(meth)acrylate,
meth)acrylate, polyglobylene glycol mono(
meth)acrylate, pentaerythritol tri(meth)acrylate, polypropylene glycol di(meth)acrylate
(Meth)acrylic acid esters having a hydroxyl group such as acrylate, methacryloxyethyl phosphate, bis(methacryloxyethyl)phosphate; dimethylcyanoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate (meth)acrylic acid esters having an amino group such as; and urethane prepolymers having an incyanate group obtained by reacting the above-mentioned (meth)acrylic acid esters having a hydroxyl group with an organic diisocyanate.

Compound or 1 having an acid anhydride group used in the present invention
One functional group that has at least one carboxyl group or a phenolic hydroxyl group and is capable of reacting with the functional group present in the reaction mixture obtained by reacting the above-mentioned (a), (b), and (c). Examples of the compound (a) having the above include succinic anhydride, phthalic anhydride, tetrabromophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, naphthalene dicarboxylic anhydride, α-methylene gluconic anhydride, and tribromophthalic anhydride. Acid anhydrides such as mellitic acid, chlorinated maleic anhydride, citraconic anhydride, itaconic anhydride; thiomaleic acid, thiosalicylic acid, thioglycolic acid, 1-carboxymethyl-5-mercapto-1,2,3,4- A compound having a carboxyl group and a thiol group, such as tetrazole, 5-carboxymethylthio-2-mercapto-1,3,4-thiadianizole.

0-Sulfamidobenzoic acid, 0-aminobenzoic acid, diaminobenzoic acids, p-aminobenzoic acid, m-aminobenzoic acid, 2-amino-4-(α-217- tro)aceticuamide-1,3- 1 riazole, 2
-Compounds having a carboxy group and an amine group, such as amino-4-aceticamido-1,3-triazole; or derivatives thereof; also having a phenolic hydroxyl group and other reactive functional groups Examples of compounds include monooxycarboxylic acids such as salicylic acid, n-oxybenzoic acid, and p-oxybenzoic acid, monooxymalonic acid derivatives such as tartotanic acid, monooxymalic acid derivatives such as malic acid and isomalic acid, and glutanic acid. Examples include monooxyglutaric acid derivatives such as 3,5-dio*cybenzoic acid (resorcinol), trioxybenzoic acid derivatives, and the like. Among the above compounds or derivatives, phthalic anhydride, maleic anhydride, trimellitic anhydride, thiomaleic acid, thioglycolic acid, and monooxydicarboxylic acids are mainly used.

Next, a typical method for synthesizing the photosensitive resin (3), which is one of the main components of the alkali-developable photosensitive resin composition, will be described.

18- (1) Reaction between chain polymer compound (a) and polyfunctional epoxy compound (b): Chain polymer compound (a) and polyfunctional epoxy compound (b)
In the reaction, component (b) is charged into a reactor at a ratio of 1 to 5 moles per equivalent of a functional group that reacts with the epoxy group or hydroxyl group of component (a), and the reaction is carried out at 80 to 180°C under a nitrogen atmosphere.
Preferably, the mixture is heated and stirred at a reaction temperature of 100 to 120°C for 2 to 10 hours. The end point of the reaction is defined as the point at which the functional groups at both ends of component (a) have almost completely disappeared. After the reaction is completed, the epoxy at present in the reaction mixture is measured and used in the formulation for the next epoxy acrylate synthesis. In the above reaction, appropriate amounts of catalysts, solvents, etc. can be used as long as they do not interfere with the reaction. If necessary, an appropriate amount of isocyanate compound may be introduced into the functional groups such as hydroxyl groups generated in the above reaction or present in components (a) and (b) to increase the molecular weight. It is also possible to measure it.

(11) Synthesis of epoxy acrylate: 0.5
~1.0% by weight of a tertiary amine catalyst, such as triethylamine, is added and, while passing through dry air, (
C) Component (meth)acrylic acid etc. is added to 0.2 to 1.
It is gradually added dropwise at a ratio of 0 mol. Reaction at 60-130℃
, preferably at a temperature of 80 to 90°C for 1 to 10 hours. To complete the reaction, measure the functional groups such as (meth)acrylic acid, especially the acid value, and stop the reaction when the value reaches 2 KOH/7 or less. If necessary, remove the unreacted (meth)
Acrylic acid may be removed under reduced pressure. Furthermore, it is confirmed that the reaction of the synthesized epoxy acrylate is progressing using z, R analysis, etc., and the process proceeds to the next step.

Song) Introduction of alkali-developable functional groups: Add the epoxy acrylate synthesized in (11) and an acid anhydride such as maleic anhydride as component (d) to 1 equivalent of the reacting functional group in the epoxy acrylate. On the other hand, the component (d) is reacted with a mixture of 0.2 to 1.0 mol of Buyu. The reaction was carried out for 60 minutes with dry air and stirring.
At a reaction temperature of ~120°C, preferably 80-90°C, 1
The reaction is carried out for 9 hours, preferably 2 to 5 hours, to synthesize a photosensitive resin. In addition, if necessary, monomers such as hydroxy (meth)acrylate that can be polymerized by irradiation with actinic rays can be added to dilute the composition. Furthermore, if necessary, it is also possible to increase the molecular weight of the photosensitive resin (8) by introducing an incyanate compound or the like to completely eliminate the stickiness after drying.

Another main component of the alkali-developable photosensitive resin composition of the present invention is a sensitizer containing a sensitizer or accelerator that starts the reaction of the photosensitive resin (3). , the amount of sensitizer used is 0.00 based on the total resin content.
1 to 20% by weight, preferably 0.5 to 10% by weight.

For example, representative compounds as sensitizers are listed: ruto, henzin, benzoin methyl ether, benzoin ethyl ether, benzoin isopro-21-biyl ether, benzoin isobutyl ether, henzin acetate, benzophenone, 2-10-rubenzophenone, 4-methoxy Benzophenone, 4,4'-dimethylbenzophenone, 4-7' Rombenzov / 7.2+
2', 414'-tetrachlorobenzophenone, 2-chloro-4'-methylbenzophenone, 3-methylbenzophenone, 4-t-butylbenzophenone, benzyl,
Benzylic acid, diacetyl, methylene blue, acetophenone, 2,2-jethoxyacetophenone, 9.10-
Phenanthrenequinone, 2-methylanthraquinone, 2
-ethylanthraquinone, 2-t-butylanthraquinone, diphenyl disulfide, dithiocarbamate,
α-Chloromethylnaphthalene, anthracene, iron chloride 1
, 4-naphthoquinone, anidron, thioxanthone,
Examples include ketals, aromatic hydrocarbons such as dimethylbenzylamine, ketones, quinones, amino compounds, nitro compounds, phenol compounds, thioxanthones, and ketals.

These can be used alone or in combination of two or more. Among these, particularly preferred are 2,2-jethoxyacetophenone, 2,2-dimethoxy-2-phenyl acetophenone, penzoin isoglobyl ether, benzoisobutyl ether 2-ethylanthraquinone, 1
, 4-diisopropylthioxanthone, 1,4-diethylthioxanthone, benzyldimethyl ketal, and the like. Further, it is advantageous to use amines or sulfur-containing compounds as accelerators in combination with the above-mentioned sensitizers because the curing rate is increased and the polymerization inhibiting effects of oxygen and the like are significantly reduced.

Such amines include primary amines such as butylamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, monoethanolamine; diethylamine, dimethylaniline, dimethyl-para-toluidine, pyridine, NIN'-dimethylcyclohexylamine, Secondary compounds such as jetanolamine, triethanolamine, triethanolamine triacrylate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, ethyl-4-dimethylaminobenzoate, 2-dimethylamine ethylbenzoate, diisopropyl dimethylaminobenzoate, etc. There are amines or tertiary amines. Mercaptans are mainly used as sulfur-containing compounds. Furthermore, the alkali-developable photosensitive resin composition of the present invention comprises a photosensitive resin (3) and a sensitizer composition [
F]) as the main component, but from the viewpoint of improving various properties and workability, photosensitive monomers (reactive monomers), photosensitive oligomers (reactive oligomer χ bonds) may be added as necessary. Also used are coloring materials such as dyes and pigments, additives such as flame retardants, polymerization inhibitors, plasticizers, leveling agents, gloss-imparting agents, fillers, and solvents. These various compounding agents are used for different purposes, but when using them, it is necessary to select those that are effective at a compounding amount that does not reduce the physical properties or sensitivity of the alkali-developable photosensitive resin composition. Of course, it is.

To give some examples of the various compounding agents mentioned above, photosensitive monomers and photosensitive oligomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (
meth)acrylate, 2-ethylhexyl(meth)acrylate, lauryl(meth)acrylate, ethylene glycol di(meth)acrylate, diprolene glycol di(meth)acrylate, triprolene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate,
meth)acrylate, polyethylene glycol mono(meth)acrylate with a polymerization degree of 1 to 20, polyethylene glycol di(meth)acrylate with a polymerization degree of 1 to 20, polypropylene glycol mono(meth)acrylate with a polymerization degree of 1 to 20, polymerization degree of 1 ~20 polypropylene glycol di(meth)acrylate, dipropylene glycol (
meth)acrylate, tripropylene glycol (meth)acrylate, 1.3-butylene glycol di(meth)acrylate, 1,6-hexanediol (meth)acrylate), 1.4-butylene glycol di(meth)acrylate, Neo Pentyl glycol di(meth)acrylate, trimethylol propane tri(meth)acrylate, pentaerythritol (
(meth)acrylate, etc. These monomers can be used alone or in combination of two or more, and among these, the photosensitive monomer is mainly used as a thinning agent to adjust the viscosity, and in the case of a polyfunctional monomer, it is used as a crosslinking agent. Examples of coloring materials such as dyes and pigments include alumina white,
Extender pigments such as clay, talc, barium sulfate, barium carbonate, etc.; Inorganic pigments such as zinc white, lead white, yellow lead, red lead, ultramarine, deep blue, titanium oxide, zinc chromate, red iron, carbon black; Gilliant carmine 6B1 Hermanent Red R1 Organic pigments such as benzidine yellow, phthalocyanine yellow, phthalocyanine blue, phthalocyanine green, and Victoria Pure Blue; and basic dyes such as Masenda and Rhodamine; direct dyes such as Direct Left Scar Red and Direct Orange; Examples include acidic dyes such as metanyl yellow.

Examples of flame retardants include inorganic flame retardants such as aluminum hydroxide, zinc borate; tetrachlorinated pen26-zene, Ogaki chlorinated benzene, chlorinated diphenyl, chlorinated triphenyl, chlorinated polyphenyl, and bacloropenta. Chlorinated products such as cyclodecane; Brominated products such as tetrabromoethane, tetrabromobutane, tetrabromoacetylene, hexabromobenzene, tribromotoluene, hexabromototicane, allyl ester of trifluorophenol, and tetrabromobisphenol A; dichloro Salt brominated compounds such as tetrabromoethane and dibromotetrafluoroethane; ) halogen-containing phosphates such as IJs (β-chloroethyl) phosphate and pentachlorophenol methacrylate, etc. can be used. especially,
In the present invention, since the coating film of the photosensitive resin composition has excellent durability and can be used as a permanent resist, flame retardancy is a very important factor. ) It is desirable to select the appropriate material carefully, taking into consideration the compatibility with the material. Further, as flame retardant aids, antimony trioxide, red phosphorus, organic amines, organic peroxides, metal oxides, etc. are used.

Examples of fillers include powdered glass, powdered silica, magnesium silicate, aluminum silicate, calcium carbonate, lipophilic silica, bentonite, and the like. However, when used as a photosensitive resin, it is generally necessary to avoid using materials that have an adverse effect on photosensitive properties such as resolution.

As the antifoaming agent, leveling agent, and gloss imparting agent, silicone wax, surfactant, silicone oil, polyethylene wax, silane coupling agent, fluorine surfactant, paraffin wax, etc. are used.

Examples of plasticizers include phthalic esters such as dibutyl phthalate and dioctyl phthalate; phosphoric esters such as tricresyl phosphate and diphenyloctyl phosphate; dibasic esters such as dibutyl sebacate, dioctyl sebacate, and di-2-ethylhexyl adipate. Esters and the like are used to lower the initial viscosity of the resin and to impart elasticity to the cured product.

The above are typical compounding agents, and these may be appropriately blended and used as necessary. The alkaline-developable photosensitive resin composition of the present invention is capable of thick film curing, and has high resolution and excellent durability. It is a resin composition with high sensitivity and excellent workability. It is also possible to improve the cured film by heating or post-curing treatment with infrared rays, ultraviolet rays, electron beams, etc. after development, but post-curing treatment after development is not particularly required. Furthermore, although the alkali-developable photosensitive resin composition of the present invention is alkali-developable, the cured coating film has excellent alkali resistance.

It also has excellent properties such as acid resistance, water resistance, solvent resistance, and weather resistance, making it most suitable not only as a temporary resist for etching purposes, but also as a permanent resist such as solder resist and metki resist in full additive methods. There is. This resist resin can be used in many fields such as etching resists related to printed wiring boards, solder resists, metallurgical resists, and letterpress resists, halftone gravure resists, cross beam roll resists, and name plate resists. In addition to its use as a photo resist, it is also used as a photosensitive resin in a wide range of fields such as 28 plates as offset printing plates, photosensitive liquids and resist inks for screen printing, general printing inks, and preservation coatings. can do.

Therefore, the alkali-developable photosensitive resin composition of the present invention is characterized by high resolution and excellent durability, and has vastly improved properties compared to conventional alkali-developable photosensitive resin compositions. , it is possible to apply it to a wide range of applications other than those mentioned above.

The alkali-developable photosensitive resin composition of the present invention can be used as an ordinary liquid photoresist material, specifically by the following method. An alkali-developable photosensitive resin composition obtained by blending a photosensitive resin composition with () and a sensitizer composition, or a blend with (3) and (3) with other additives, is used as a glass material. 30 types including base epoxy resin board, paper base phenol resin board, paper base epoxy resin board, copper plate aluminum board, stainless steel board, various plastic boards, polyester film, polyolefin film, polyimide film, etc.
- 1-500 μm preferably 15-150 μm on the substrate
The resist is applied using a coating method such as a roll coater, curtain flow coater, spinner, wheeler, or tipping to a coating thickness of .

Next, the film formed on the substrate is pre-cured at a temperature of room temperature to 120°C, preferably 40 to 80°C, to remove stickiness and make it tack-free. Next, the pattern film is vacuum-deposited on the dry coating plate, and in order to crosslink the coating by light irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultralight pressure mercury lamp, a carbon arc lamp, a xenon lamp, a tungsten lamp, a metal halide lamp, a sodium lamp are used. ,
A light source such as a tungsten halogen lamp or an ultraviolet fluorescent lamp is used to generate actinic rays with wavelengths of 200 to 800 nm, which are irradiated as parallel rays. The irradiation time varies depending on the irradiation conditions such as the light source used and the irradiation distance, but is usually 10 to 15,000 mj/cFlf.

The thin solution) is maintained at a temperature of 10 to 30 DEG C., preferably 20 to 25 DEG C., and developed using a commercially available developer or ultrasonic cleaner, and immediately washed with a large amount of washing water after development. Next, if necessary, 150-180°C, preferably 100-180°C.
Post cure for 30 minutes at a temperature of 150°C. In the above method, the coating thickness is 1 to 10 μm with a coating thickness of 15 to 150 μm.
It is possible to form a fine pattern on the order of m.

Hereinafter, the present invention will be further explained in detail with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these Examples in any way. Furthermore, parts and parts in the examples indicate parts by weight and weight %.

Synthesis Example 1 In a reaction flask equipped with a stirrer, a thermometer, a gas inlet tube, a dropping device, and a condenser, polybutadiene having carboxyl groups at both ends of the molecule [manufactured by Nippon Soda, trade name: Nl]
5SO-PBC-1000, number average molecular month, t 550
．． 1,2-vinyl bond 907%, acid value 59,8KOH1
71y/g) of (1-A) to 1000 parts of bisphenol A diglycidyl ether type epoxy resin (manufactured by Yuka Shell Epoxy ■, trade name: Ebico) 828).
1,000 parts of the mixture was charged, and while nitrogen gas was introduced little by little into the reaction flask and the mixture was stirred, the reaction was carried out at 130 to 140°C for 7 hours. The acid value of the reaction mixture was 3 or less, and a polybutadiene-modified epoxy resin (1-B) with an epoxy commercial amount of 483 was obtained.
I got it.

Next, 370 parts of methacrylic acid, 3 parts of hydroquinone monomethyl ether, and 10 parts of triethylamine were added,
Switch the nitrogen gas in the reaction flask to dry air and incubate for 80 minutes.
The mixture was heated and stirred at °C for 10 hours to obtain a polybutadiene-modified unsaturated resin (1-C).

Next, after diluting with 2000 parts of methyl ethyl ketone,
250 parts of maleic anhydride was added, and the mixture was heated and stirred at 80° C. for 3 hours to obtain a maleic acid adduct (1-D) of (1-C).

Synthesis Example 2 Polybutadiene-modified epoxy resin obtained in Synthesis Example 1 (
1-B) To 2,000 parts, add 3 parts of hydroquinone monomethyl ether and 10 parts of triethylamine, and heat to 80°C with stirring while passing dry air little by little. Then, add 310 parts of acrylic acid 33- for 1 to 2 hours. The mixture was added dropwise, and the mixture was heated and stirred at 80° C. for 10 hours to obtain a polybutadiene-modified unsaturated resin (2-C).

Next, after diluting with 2000 parts of butyl acetate,
250 parts of maleic anhydride was added, and the mixture was heated and stirred at 80° C. for 3 hours to obtain a maleic acid adduct (2-D) of (2-C).

Synthesis Example 3 Polybutadiene-modified unsaturated resin obtained in Synthesis Example 2 (2
-C) 1000 parts of butyl acetate
300 parts of phthalic anhydride were added, and the mixture was heated and stirred at 80°C for 3 hours to obtain a phthalic acid adduct (3-D) of (2-C).

Synthesis Example 4 Polybutadiene-modified unsaturated resin obtained in Synthesis Example 2 (2
-C) 1000 parts of butyl acetate
150 parts of itaconic anhydride were added thereto, and the mixture was heated and stirred at 80° C. for 4 hours to obtain an itaconic acid adduct (4-D) of (2-C).

Synthesis Example 5 -34=Nl5SO-PBC-1000 in the same manner as Synthesis Example 1
8282,000 parts of Epikote was reacted with 1,000 parts of the sample at 130 to 140° C. for 6 hours while stirring under a nitrogen stream. The acid value of the reaction mixture was 3 or less, and a polybutadiene-modified epoxy resin (5-B) with an epoxy equivalent of 325 was obtained.
I got it.

Next, 6 parts of Hydrogen 2F and 15 parts of triethylamine were added, and the mixture was heated to 80°C while stirring while gradually introducing dry air.
700 parts of acrylic acid was added dropwise over about 2 hours, and the mixture was further heated and stirred at 80° C. for 10 hours to obtain a polybutadiene-modified unsaturated resin (5-C). Next, after diluting with 2000 parts of methyl isobutyl ketone, 500 parts of maleic anhydride was added, and the mixture was heated and stirred at 80°C for 3 hours (5-C
) was obtained as a maleic acid adduct (5-D).

Synthesis Example 6 10 of Nl5SO-PBC-1000 used in Synthesis Example 1
00 parts, Epicoat 828,500 parts, bisphenol A diglycidyl ether type epoxy resin (manufactured by Yuka Shell Epoxy ■, trade name: Ebiko) 1001) 5
00 parts and 5 parts of N,N-dimethylbenzylamine were charged into a reaction flask, and while nitrogen gas was passed little by little into the flask and the mixture was stirred, the reaction was carried out at 120° C. for 4 hours. The acid value of the reaction mixture became 1 or less, and a polybutadiene-modified epoxy resin (6-B) with an epoxy equivalent of 760 was obtained.

Next, 5 parts of hydroquinone monomethyl ether was added, and the nitrogen gas in the reaction flask was replaced with dry air.
After heating to 0°C, 190 parts of acrylic acid was added dropwise over 1 hour, and the mixture was further heated and stirred at 80°C for 8 hours to obtain a polybutadiene-modified unsaturated resin (6-C).

Next, after diluting with 2000 parts of methyl ethyl ketone,
200 parts of maleic anhydride was added, and the mixture was heated and stirred at 80° C. for 3 hours to obtain a maleic acid adduct (6-D) of (6-C).

Synthesis Example 7 Nl5SO-PBC-1000-10 used in Synthesis Example 1
00 parts, alicyclic epoxy resin (manufactured by UCC, trade name: Bakelite ERL-4221,) 1300 parts
A portion of the mixture was placed in a reaction flask, and the mixture was reacted at 120° C. for 3 hours while stirring under a nitrogen stream. The acid value of the reaction mixture is 1
A polybutadiene-modified epoxy resin (7-B) having an epoxy equivalent of 248 was obtained as follows.

Next, 3 parts of hydroquinone monomethyl ether and 10 parts of triethylamine were added, the nitrogen gas in the reaction flask was changed to dry air and the temperature was heated to 80°C, and then 670 parts of acrylic acid was added dropwise over 2 hours, and the mixture was further heated at 80°C for 14 hours. Continuing to heat and stir for hours, polybutadiene-modified unsaturated resin (7-
C) was obtained.

Next, after diluting with 2000 parts of methyl ethyl ketone,
450 parts of maleic anhydride was added, and the mixture was heated and stirred at 80° C. for 3 hours to obtain a maleic acid adduct (7-D) of (7-C).

Synthesis Example 8 Polybutadiene-modified unsaturated resin obtained in Synthesis Example 2 (2
-C), 1000 parts of methyl ethyl ketone, and 100 parts of maleic anhydride were charged into a reaction flask, and heated and stirred at 80°C for 3 hours in an atmosphere of dry air (2-
A maleic acid adduct (8-D) of C) was obtained. Next, the reaction solution was cooled to 50°C,
Tolylene diisocyanate (80% 2,4-TDll
70 parts of 2,6-TDI) were added dropwise and aged at 50°C for 3 hours to form a urethane compound (8-E
) was obtained.

Synthesis Example 9 770 parts of 2-hydroxyethyl acrylate was added dropwise to 1000 parts of tolylene diisocyanate (previously described) at 50°C under a nitrogen stream, and after completion of the dropwise addition, an aging reaction was performed for 1 hour to obtain T.
A DI-HEA adduct (9-A) was obtained. Next, to 1000 parts of (8-D) obtained in Synthesis Example 8, (9
85 parts of -A) were added dropwise at 50°C, and the mixture was aged for 1 hour to obtain a urethane compound (9-E).

Synthesis Example 10 Polybutadiene-modified unsaturated resin obtained in Synthesis Example 2 (2
-C) 1,000 parts and 1,000 parts of methyl ethyl ketone were mixed in a nitrogen atmosphere, and while maintaining the temperature at 50°C, 25 parts of tolylene diisocyanate (mentioned above) was added dropwise.
A 38-urethane compound (10-E) was obtained by aging at ℃ for 1 hour. Next, 710 parts of maleic anhydride was added and stirred at 80°C for 3 hours (10-
A maleic acid adduct (10-D) of E) was obtained.

Synthesis Example 11 In Synthesis Example 1, using 250 parts of maleic anhydride, 8
(1-C) was carried out in exactly the same manner except that instead of reacting at 0°C, 235 parts of thioglycolic acid was used and the reaction was carried out at 60°C.
A thioglycolic acid adduct (11-D) was obtained.

Synthesis Example 12 In a reaction flask similar to that used in Synthesis Example 1, polybutadiene having a hydroxyl group at the molecular end (manufactured by Nippon Soda ■, trade name: Nl5OO-PBG-1000, number average molecular weight 1390, hydroxyl value 68.3. 1,2-vinyl bond 91
1ch) 1,000 parts of dioxane and 1,000 parts of dioxane were charged and dissolved, and heated to 80°C while stirring under a nitrogen atmosphere. Then, 1,000 parts of mercaptoethyl alcohol was added dropwise over about 1 hour, and after the dropwise addition was completed, the mixture was heated to 80°C. The reaction continued for 7 hours.

Next, unreacted mercaptoethyl alcohol and dioxane were removed by distillation under reduced pressure at 100°C for 2 hours to obtain a reaction product (C-
1-a) was obtained. Next, the above reaction product (C-1-a
) was dissolved in 1000 parts of pyridine, and 193 parts of cinnamylidene acetic acid chloride and 100 parts of pyridine were dissolved therein.
A brown precipitate was obtained, which was thoroughly washed with water, dried, and diluted with methyl ethyl ketone to obtain a photosensitive resin (C-1-b) having a solid concentration of 50 parts.

Examples 1 to 11 (1-D) to (7-D) obtained in Synthesis Examples 1 to 11, (
10-D), adduct of (11-D), or (8-E)
, (9-E) were used to obtain alkali-developable photosensitive resin compositions having a solid concentration of 50% using the various formulations shown in Table 1. A dry coating film of about 20% is coated on a polyester film prepared by applying the above-prepared photosensitive resin composition.
It was applied to a thickness of 0 μm and dried with hot air at 80°C for 30 minutes to obtain a test piece. Using this test piece, solubility in alkaline solutions, adhesion of the film surface, development sensitivity and resolution were tested. Ta. On the other hand, a dry film was applied to a glass base epoxy board to a thickness of about 30 μm,
Development, sensitivity, resolution, and coating film physical properties were tested using test pieces obtained by drying with hot air at 80° C. for 30 minutes. The results are shown in Table 2.

Comparative Example 1 Using the (12-D) resin obtained in Synthesis Example 12, a comparative photosensitive resin composition with a solid concentration of 50% was obtained with the various formulations shown in Table 1, and the test was conducted in the same manner as in the example. Ta. The results are shown in Table 2. However, in this test, a thin film (5-7 μm) was used because the thick film was not sufficiently cured due to the same uncured condition as in the example.

41- -712- Test method> (1) Coating surface adhesive photosensitive resin composition was applied to a grained polyester film and a glass base epoxy board (FR-4) with a dry coating of 20 to 3
It was applied to a thickness of 0 μm, dried in a hot air dryer at 80° C. for 30 minutes, and the tackiness was determined by touching the surface of the formed film on the test plate with a finger.

(11) Solubility in alkaline solution A polyester film test piece or a glass-based epoxy board (FR-4) test piece prepared under the same conditions as in section (1) was heated in a 1% sodium hydroxide solution at 20°C. The solubility of the film is examined by immersing it in a 1% potassium hydroxide solution.

(iii+Development and sensitivity (1) Similar to the above, the dry film of the photosensitive resin composition was
Apply with a spinner to a thickness of 30 μm, and
A Kodak Step Tablet Swallow 2 was vacuum-adhered onto the test specimen film that had been dried with hot air at 0°C for 30 minutes, and a light source device for photoresist exposure (Phoenix-3000 manufactured by Oak Co., Ltd.,
A light amount of 434 3-100/i was irradiated using an ultra-high pressure mercury lamp (water-cooled). Using 1T sodium hydroxide solution as a developer, the film was developed for 30 seconds in an ultrasonic cleaner at a solution temperature of 20°C, and the developability and sensitivity (bottom curing light amount) were examined.

(lv) Resolution After vacuum-adhering a dot chart onto the test piece film prepared in the same manner as in (1) above and irradiating it with a light intensity of 100 mj/cri using a light source for photoresist exposure, Develop under the same conditions as in item i10 and observe the resolution.

(v) Coating film physical properties Create a specimen by irradiating a film formed on a glass base epoxy plate prepared in the same manner as in section (11) with a light intensity of 100 mj/c using a light source device for photoresist exposure. .

■Hardness Measured according to JIS-D-0202 @Adhesion to board" The specimen described in "2" was cut in a goblin and evaluated by Sellotape peeling test θ Soldering heat resistance 44- The above specimen was placed in a solder bath at 260°C for 30 seconds. Observe the appearance when soaked.

O Chemical resistance A test piece is immersed in a chemical under the following conditions, and judged based on appearance and adhesion.

Acid resistance: 10 HC1 (50℃ x 10 hours), base resistance: 10% NaOH (50℃ x 10 hours), water resistance: 10
0℃ x 1 hour, Solvent resistance: Triclean (50℃ Manabu Shiga, Commissioner of the Japanese Patent Office 1, Indication of the case, Patent Application No. 230385, filed in 1982, 2, Name of the invention: Alkaline developable photosensitive resin composition 3, Person making the amendment Relationship to the case Patent applicant: 100 Chiyoda, Tokyo 2-2-1 Otemachi (430)
) Nippon Soda Co., Ltd. Representative: Niio Sannomiya 4, Agent ■ 100 2-2-1 Otemachi, Chiyoda-ku, Tokyo Nippon Soda Co., Ltd. Telephone: (245) 6234 (1) Specification Column for detailed description of the invention 6. Contents of amendment (1) rHy c a r- on page 13, line 8 of the specification
Correct CTBNJ to rHycar r-ATBNJ.

(2) rHyc, ar-HT on page 13, line 9 of the specification
Correct BJ to rHycar-HTBNJ.

(3) Line 7 from the bottom of page 31 of the specification “200-800m
μ'' is corrected to r 200-800 nmj.

(4) Line 6 from the bottom of page 41 of the specification r (12-D)J
is corrected to r(C-1-b)J.

2-

Claims (3)

[Claims] (1) Photosensitive resin: Photosensitive resin obtained by reacting the following (a), (b), (c) and (d), (a) having a functional group that reacts with an epoxy group or a hydroxyl group at both ends of the molecule. a chain polymer compound with a number average molecular weight of 500 to 2QOOO; (b) one or more epoxy compounds selected from polyfunctional epoxy compounds having an aromatic ring and alicyclic polyfunctional epoxy compounds; (c) One functional group has at least one double bond that can be polymerized by irradiation with actinic rays, and can react with the functional group present in the reaction mixture of (a) and (b) above.
(d) a compound having an acid anhydride group or one or more carboxyl groups or phenolic hydroxyl groups, and the reaction obtained by reacting the above (a), (b) and (c); A compound having one or more functional groups capable of reacting with a functional group present in the mixture; 03) A sensitizer that initiates the reaction of the photosensitive resin by irradiation with actinic rays, or a sensitizer containing an accelerator. An alkali-developable photosensitive resin composition comprising the above-mentioned compounds and @) as main components. (2) The photosensitive resin composition according to claim 1, wherein component (a) is a compound selected from the group having carboxyl groups, amino groups, thiol groups, isocyanate groups, and hydroxyl groups at both ends. (3) In the reaction of components (a), (b), (c), and (d), 1) Component (b) is added to 1 equivalent of the functional group that reacts with the epoxy group or hydroxyl group of component (a). 1
~5 mol, 11) 0 of (C) per equivalent of noethoxy group in the reaction mixture obtained by reacting (a) and (b).
2 to 1.0 mol, li+) Component (d) is reacted at a reaction rate of 0.2 to 1.0 mol with respect to 1 equivalent of the reactive functional group of the epoxy acrylate compound obtained in II) above. The photosensitive resin composition according to any one of claims 1 to 2, which is a photosensitive resin obtained.