KR101356950B1 - Photosensitive resin composition - Google Patents

Abstract

An object of the present invention is to provide a photosensitive resin composition which has a developing characteristic which can be used in a photolithography process and which can form a cured coating film excellent in heat resistance, adhesion and transparency, and which comprises a polymer component (A) and a photopolymerizable monomer. A photosensitive resin composition comprising (B), wherein the polymer component (A) may have a polymerizable monomer (a-1) having two or more hydroxyl groups in the molecule and a crosslinked structure having 6 to 20 carbon atoms in the molecule. It is a photosensitive resin composition which is a polymer containing the monomer component which has a polymeric monomer (a-2) which has a frame | skeleton.

Description

[0001] PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a photosensitive resin composition. More specifically, in the photosensitive resin composition which can form the cured coating film excellent in heat resistance, adhesiveness with a board | substrate, and image development property which can be used suitably for a soldering resist, various coatings, an adhesive agent, a printing ink binder, a color filter binder, etc. It is about.

Recently, radiation curable resins that can be cured with ultraviolet rays or electron beams are widely used in the fields of printing, coating, and adhesives from the viewpoint of resource saving and energy saving. Solder resists are also used in the field of electronic devices such as printed wiring boards to protect circuit boards after component mounting for a long time. Acid-pendant novolac epoxy acrylate is generally used as a printed wiring board in the photoresist method, but adhesiveness with copper plating is not sufficient, and when used for a multilayer printed wiring board, sufficient between conductor circuits is used. In addition to having the problem of not being able to obtain adhesion strength, they also had the problem of being easily cracked because of their poor flexibility.

In order to solve these problems, the method of mixing an inorganic filler with the photosensitive resin composition using a (meth) acryl copolymer is proposed (for example, patent document 1), but compared with acid pendant type novolak epoxy acrylate There was problem to fall.

Although a color filter is used for a color liquid crystal display device or a solid-state image sensor, these are the colored coating film which colored the red (R), green (G), blue (B) etc. in a predetermined pattern on the board | substrate, and between them. Of black matrix. Usually, it forms by forming a black matrix on transparent substrates, such as glass, and then forming colored coating film patterns, such as R, G, and B, sequentially.

In general, color filters are manufactured by a manufacturing method such as dyeing, printing, pigment dispersion, or electrodeposition. Among them, the photolithographic method is applied on a transparent substrate using a photocurable resin composition mainly composed of alkali-soluble resins, reactive monomers, photopolymerization initiators, pigments and solvents, and repeating exposure, development, and post curing. The pigment dispersion method produced by the present invention has become mainstream because of its excellent durability, such as light resistance and heat resistance, and fewer defects such as pinholes.

While the pigment dispersion method has the above advantages, since the patterns such as the black matrix, R, G, and B are repeatedly formed, high heat resistance and adhesion to the substrate are required for the alkali-soluble resin serving as the binder of the coating film.

By the method of improving the heat resistance of alkali-soluble resin, the resin composition (for example, patent document 2) which uses conventionally the (meth) acrylic acid ester which has a cyclic structure in a side chain as a copolymerization component, and the monomer containing maleimide Resin compositions (for example, patent document 3) etc. which make a copolymerization component are proposed.

However, in the resin composition which uses the (meth) acrylic acid ester which has a cyclic structure in an electron side chain as a copolymerization component, when the use ratio is increased in order to improve heat resistance, it may be a problem that adhesiveness with a board | substrate falls, or in a developing process. Problems such as a decrease in the solubility of the resin in the developer to be used, a long time for the developing process, a development becomes impossible, and a predetermined pattern cannot be obtained, or heating performed to fix the coating film even if a pattern is obtained. There was a problem that the side chains were pyrolyzed at the time of post-curing treatment to become volatile components, contaminating the production line.

The resin composition comprising the latter maleimide as a copolymerization component is colored from yellow to yellow brown due to the nitrogen atom contained in the molecule, thereby deteriorating the transparency of the coating film. Moreover, there existed a problem that coloring progresses further at the time of post-cure which heat-processes.

Patent Document 1: Japanese Patent Application Laid-Open No. 2006-190848

Patent Document 2: Japanese Patent Application Laid-Open No. 2004-240396

Patent Document 3: Japanese Patent Application Laid-Open No. 2003-29018

Problems to be solved by the invention

An object of this invention is to provide the photosensitive resin composition which has the image development characteristic which can be used for a photolithography process, and can form the cured coating film excellent also in heat resistance, adhesiveness, and transparency.

Means for solving the problem

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the said subject. As a result, an essential component is a polymerizable monomer (a-1) having two or more hydroxyl groups in a molecule and a polymerizable monomer (a-2) having an alicyclic skeleton which may have a crosslinked structure having 6 to 20 carbon atoms in the molecule. It was found out that the resin composition containing the copolymer contained therein could solve the above problems, and completed the present invention based on this finding.

That is, the photosensitive resin composition of this invention is a photosensitive resin composition containing a polymer component (A) and a photopolymerizable monomer (B), and a polymerizable monomer (a-) in which a polymer component (A) has two or more hydroxyl groups in a molecule | numerator. It is characterized by being a copolymer containing 1) and the monomer component which has a polymerizable monomer (a-2) which has an alicyclic skeleton which may have a C6-C20 crosslinked structure in a molecule | numerator.

Effects of the Invention

According to this invention, the photosensitive resin composition which has the image development characteristic which can be used for a photolithography process, and can form the cured coating film excellent also in heat resistance, adhesiveness, and transparency can be provided.

Moreover, the cured coating film formed from the photosensitive resin composition of this invention is excellent in heat resistance and adhesiveness with respect to a glass substrate and a semiconductor substrate, and since it has alkali developability, it is very useful in various resist fields.

PREFERRED EMBODIMENTS FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The photosensitive resin composition of this invention has a polymerizable monomer (a-1) which has a 2 or more hydroxyl group in a molecule, and the polymerizable monomer (a-2) which has an alicyclic skeleton which may have a C6-C20 crosslinked structure in a molecule | numerator. By including as a polymer component (A) the copolymer which consists of a monomer component which becomes an essential component, it has the image development characteristic which can be used for a photolithography process, and can form the cured coating film excellent in heat resistance, adhesiveness, and transparency. .

Hereinafter, the polymer component (A) will be described.

The polymerizable monomer (a-1) having two or more hydroxyl groups in the molecule is not particularly limited, but specific examples thereof include glycerol mono (meth) acrylate, butane triol mono (meth) acrylate, and pentane triol mono (meth). Alkylene polyol mono (meth) acrylates, such as a) acrylate, caffeic acid, a shimic acid, etc. are mentioned. Among these, glycerol mono (meth) acrylate is preferable at the point of adhesiveness and image development characteristics.

Although the ratio of the polymerizable monomer (a-1) which has two or more hydroxyl groups in the molecule | numerator in a monomer component at the time of obtaining the said polymer component (A) is not restrict | limited, 3-30 mol% in all monomer components, Preferably Is 5-20 mol%, More preferably, it is 5-15 mol%. When the said polymerizable monomer (a-1) exists in this range, since coating-film performances, such as adhesiveness, are also enough, since the introduction amount of hydroxyl group is maintained moderately, the viscosity of the photosensitive resin composition solution does not become high and the ratio of the solvent in the photosensitive resin composition Since there is no need to increase the degree of freedom, the degree of freedom of blending can be maintained. Moreover, since the compounding ratio of other monomers can be made relatively high, the amount of introduction of the carboxyl group required for alkali development described later and the photosensitive group required for photocuring is not limited without reducing heat resistance.

Since the said polymerizable monomer (a-1) has a high function of providing developability and adhesiveness, since a blending ratio is at least, the polymerizable monomer which gives relatively heat resistance, the polymerizable monomer which gives developability, and photosensitive property are provided. The compounding ratio of the polymerizable monomer to be made can be increased, and it becomes possible to make both developability and photosensitivity as a polymer component (A) compatible with heat resistance and adhesiveness.

As a polymerizable monomer (a-2) which has an alicyclic skeleton which may have a C6-C20 crosslinked structure in a molecule | numerator, the concrete example is cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, ethyl Cyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, 1,4-cyclohexane dimethanol mono (meth) acrylate, tricyclodecanyl (meth) acrylate, tricyclodecanyloxyethyl (meth ) Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, rosin (meth) acrylate, (Meth) acrylates, such as norbornyl (meth) acrylate, 5-methyl norbonyl (meth) acrylate, and 5-ethyl norbornyl (meth) acrylate; monoterpenes having C-C double bonds in molecules such as α-pinene and α-tapineol; Cycloalkenes such as norbornene, 5-methylnorbornene, 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid anhydride, and the like. Can be. Among these, cyclohexyl (meth) acrylate, tricyclo decanyl (meth) acrylate, rosin (meth) acrylate, and norbornene are particularly preferable in terms of heat resistance.

Although the ratio of the polymerizable monomer (a-2) which has an alicyclic skeleton which may have a C6-C20 crosslinked structure in the molecule | numerator in a monomer component at the time of obtaining the said polymer component (A) is not specifically limited, All monomers 3-30 mol%, Preferably it is 5-20 mol%, More preferably, it is 5-15 mol% among components. When compound (a-2) is in this range, the compounding ratio of other monomers does not become relatively low, adhesiveness with a board | substrate becomes enough, and the introduction amount of the carboxyl group required for alkali image development mentioned later, and the photosensitive group required for photocuring is introduced. There is no limit to this. Moreover, since the introduction amount of the alicyclic skeleton which may have a crosslinked structure does not increase, the solubility of the resin in the developing solution does not decrease, the time taken for the developing step does not become long, and the development is not impossible, and a predetermined pattern is not obtained. You can get it. Moreover, coating film performances, such as heat resistance, also become enough.

The polymer component (A) has an acid value of 20 to 180 mgKOH / g, preferably 30 to 150 mgKOH / g, more preferably 40 to 140 mgKOH / g.

If the acid value is within this range, sufficient alkali development characteristics can be obtained. That is, when the acid value is within this range, the solubility in the alkaline developer is sufficient, so that the hardened portion is not dissolved or swelled in the alkaline developer.

It is preferable that the said polymer component (A) is 5000-80000 with a weight average molecular weight (number of polystyrene conversion by GPC method). If the weight average molecular weight is within this range, there is no decrease in heat resistance or solubility, and solubility in an alkaline developer is also sufficient.

In order to introduce an acid value into the polymer component (A), unsaturated monobasic acid (a-3) is used as a copolymerization component (copolymer (A-1), copolymer (A-2)), or a radical having an epoxy group. After reacting unsaturated monobasic acid (a-3) with the epoxy group of the copolymer using the polymerizable compound (a-5) as a copolymerization component, the polybasic acid anhydride (a) is produced in the hydroxyl group or the hydroxyl group of the copolymerization component (a-1). -6) is known to react (copolymer (A-3)).

Copolymer (A-1) can be obtained by copolymerizing (a-1) with (a-2), (a-3) and (a-4), but the copolymerization ratio of (a-1) is the total monomers. 3-30 mol% of components, Preferably 5-20 mol%, More preferably, 5-15 mol%, (a-2) is 3-30 mol%, Preferably 5-20 mol%, More preferably Preferably 5 to 15 mol%, (a-3) is 20 to 70 mol%, preferably 20 to 60 mol%, more preferably 20 to 50 mol%, and (a-4) is 0 to 75 mol% Preferably it is 20-60 mol%, More preferably, it is 25-50 mol%, and the sum total is 100 mol%.

It is as above-mentioned to make (a-1) 3-30 mol% and (a-2) 3-30 mol%.

(a-3) is used in order to make an acid value by having a carboxyl group exist in the side chain of copolymer (A-1). It does not specifically limit as unsaturated monobasic acid which is (a-3) of this invention, For example, (meth) acrylic acid, crotonic acid, cinnamic acid, etc. are mentioned. Moreover, polyfunctional (meth) acrylate (For example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl which has one hydroxyl group and one or more (meth) acryloyl group) (Meth) acrylate, trimethylolpropane di (meth) acrylate, etc.) and the reaction product of polybasic acid anhydride, etc. can also be used. Among these, (meth) acrylic acid is preferably used. These may use together 1 type (s) or 2 or more types.

As radically polymerizable compounds (a-4) other than (a-1), (a-2), and (a-3), if it has an ethylenically unsaturated group, it will not specifically limit. Specific examples thereof include dienes such as butadiene, 2,3-dimethylbutadiene, isoprene and chloroprene; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert -Butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl ( Meta) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, piperonyl (meth) Acrylate, salicylic (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, phenethyl (meth) acrylate , Cresyl (meta) Acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl ( Meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 (Meth) acrylic acid esters such as hydroxypropyl (meth) acrylate, naphthalene (meth) acrylate and anthracene (meth) acrylate; (Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N-di (Meth) acrylic acid amides such as iso-propylamide and (meth) acrylic anthracenylamide; Vinyl compounds such as (meth) acrylic acid acrylate, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine and vinyl acetate; Styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide derivatives of styrene; Unsaturated dicarboxylic acid diesters such as diethyl citrate, diethyl maleate, diethyl fumarate and diethyl itaconic acid; Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; N- (meth) acryloyl phthalimide etc. are mentioned. Among the above, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, styrene or vinyltoluene are preferably used from the viewpoint of the adhesiveness and transparency of the cured coating film. These may use together 1 type (s) or 2 or more types.

The radical copolymerization reaction for obtaining copolymer (A-1) is not specifically limited, The conventional radical polymerization method conventionally performed can be applied. For example, in the organic solvent which does not have a functional group, such as propylene glycol monomethyl ether and glycol ether type solvents, such as propylene glycol monomethyl ether acetate, hydrocarbon type, such as toluene and xylene, and ethyl acetate, (a-1), (a-2) Preferably, the copolymerization component of (a-3) and (a-4) is melt | dissolved in a desired ratio, and azobisisobutyronitrile, azobisvaleronitrile, benzoyl peroxide, t-butylperoxy An organic solvent solution of the copolymer (A-1) can be obtained by mixing a polymerization initiator such as 2-ethylhexanoate and polymerizing the mixture at about 50 to 130 ° C. for about 1 to 20 hours in a reflux state. The usage-amount of a polymerization initiator is about 0.5-20 weight part normally with respect to 100 weight part of total amounts of (a-1), (a-2), (a-3), and (a-4), Preferably it is 1.0-10 weight It is wealth.

You may perform block polymerization only with (a-1), (a-2), (a-3) and (a-4) and a polymerization initiator, without using an organic solvent.

The amount of the organic solvent used is usually about 30 to 1000 parts by weight, preferably 50 to 800 parts by weight based on 100 parts by weight of the total amount of (a-1), (a-2), (a-3) and (a-4). It is wealth. By setting the amount of the organic solvent to 1000 parts by weight or less, the molecular weight of the copolymer (A-1) is prevented from being lowered by the chain transfer action, and the solid content concentration of the finally obtained copolymer (A-1) is in an appropriate range. I can regulate it.

By setting it as 30 weight part or more, abnormal polymerization reaction can be prevented and a stable polymerization reaction can be advanced and it can prevent resin from coloring or gelatinizing.

The copolymer (A-1) of the present invention is a photosensitive resin composition obtained by mixing a reactive diluent or a solvent to be described later. The copolymer (A-1) is mainly used as an electronic material such as a resist. In preparing, a glycol ester solvent such as propylene glycol monomethyl ether acetate is preferably used.

Copolymer (A-2) copolymerizes (a-1), (a-2), (a-3) and (a-4), reacts the component (a-5) with the carboxyl group in the obtained copolymer, Obtained. The copolymerization ratio of (a-1), (a-2), (a-3) and (a-4) is the same as that of the copolymer (A-1), but also the carboxyl group present in the side chain (a-5) A part of the carboxyl groups is converted into an unsaturated group by reacting a radically polymerizable compound having a phosphorus epoxy group. The usage-amount of the radically polymerizable compound which has an epoxy group of (a-5) is 5-80 mol with respect to 100 mol of carboxyl groups which exist in the side chain of a copolymer. By adjusting it to 5-80 mol, the balance of a carboxyl group and an unsaturated group is good, and the curability of a copolymer (A-2) and developability by alkali are suitably maintained.

The copolymerization reaction of (a-1), (a-2), (a-3) and (a-4) can be made to react on the same conditions as copolymer (A-1).

It does not specifically limit as a radically polymerizable compound which has an epoxy group of (a-5), For example, 3, 4- epoxycyclohexyl methyl (which has glycidyl (meth) acrylate and a cyclic epoxy ( Meta) acrylate and its lactone adducts [for example, cyclomer A200, M100 by Daicel Chemical Industries, Ltd.], 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate Mono (meth) acrylic acid esters, epoxides of dicyclopentenyl (meth) acrylate, epoxides of dicyclopentenyloxyethyl (meth) acrylate, and the like, but glycidyl due to the availability of raw materials (Meth) acrylate and 3, 4- epoxycyclohexylmethyl (meth) acrylate are used preferably. These may use together 1 type (s) or 2 or more types.

In order to make a radically polymerizable compound which has an epoxy group of (a-5) react with the carboxyl group in a copolymer, it carries out as follows. That is, in order to prevent gelation by the polymerization of unsaturated monobasic acid or the resulting unsaturated group-containing copolymer, in the presence of a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, oxygen, and the like 3 In the presence of a catalyst such as a quaternary amine, a quaternary ammonium salt such as triethylbenzyl ammonium chloride, a phosphorus compound such as triphenylphosphine, and a chelating compound of chromium, the reaction is usually performed at about 50 to 150 ° C, preferably at 80 to 130 ° C. Is carried out. When the organic solvent is used in the radical copolymerization reaction for obtaining a copolymer, it can be used for subsequent reaction as it is in the state of a copolymer organic solvent solution.

The copolymer (A-3) copolymerizes (a-1), (a-2), (a-5) and (a-4), and reacts (a-3) with the epoxy group in the obtained copolymer. It is obtained by making (a-6) which is a polybasic acid anhydride react with the hydroxyl group produced | generated and the hydroxyl group of (a-1). The copolymerization ratio of (a-1), (a-2), (a-5) and (a-4) is (a-1) in the range of 3 to 30 mol%, preferably 5 to 20 mol of all monomer components. %, More preferably 5 to 15 mol%, (a-2) is 3 to 30 mol%, preferably 5 to 20 mol%, more preferably 5 to 15 mol%, (a-5) is 30 ~ 85 mol%, preferably 30-70 mol%, more preferably 30-60 mol%, (a-4) is 0-65 mol%, preferably 15-55 mol%, more preferably 25 50 mol%, and the sum total is 100 mol%.

It is as above-mentioned to make (a-1) 3-30 mol% and (a-2) 3-30 mol%.

(a-5) introduce | transduces an epoxy group into the side chain of a copolymer, and reacts with a carboxyl group of (a-3) later, and is used for introducing an unsaturated group. Moreover, it is used also for introduction of an acid value by making (a-6) which is polybasic acid anhydride react with the hydroxyl group produced | generated. Therefore, although the function differs from (a-5) introduce | transduced into the side chain of copolymer (A-2), although the introduction amount is also different, the same epoxy compound can be used.

By setting (a-5) to 30 to 85 mol%, the introduction amount of the epoxy group, that is, the introduction amount of the unsaturated group derived from the unsaturated monobasic acid of (a-3) can be adjusted, and the curability of the copolymer (A-3) Can be adjusted. By setting (a-1), (a-2) and (a-5) to the above ratio, (a-4) can be suitably selected within the range of 0-65 mol%.

The copolymer (A-3) is a radical copolymerization of the above (a-1), (a-2), preferably (a-5) and (a-4) to form a copolymer, and then (a- It can obtain by making unsaturated monobasic acid of 3) react, and then reacting anhydrous polybasic acid of (a-6). The carboxyl group of the unsaturated monobasic acid of (a-3) reacts with the epoxy group of the side chain derived from (a-5) to ring-open an epoxy group, and a hydroxyl group is formed and an unsaturated group is given to the terminal. The polybasic acid anhydride of (a-6) reacts with the hydroxyl group produced by the reaction of the hydroxyl group of (a-1) or the carboxyl group in (a-3) and the epoxy group of the side chain derived from (a-5), and the acid anhydride group is ring-opened. Converted to a carboxyl group.

The amount of the unsaturated monobasic acid (a-3) to be used is 10 to 100 moles, preferably 30 to 100 moles, more preferably 50 to 100 moles, relative to 100 moles of the epoxy group of the side chain derived from (a-5). .

The copolymer of this invention obtained by making the usage-amount of unsaturated monobasic acid into 10 mol or more introduce the minimum amount of the unsaturated group required for resin to harden, and making the usage-amount of unsaturated monobasic acid into 100 mol or less (A- The amount of unreacted unsaturated monobasic acid in 3) can be reduced.

The usage-amount of the polybasic acid anhydride of (a-6) made to react is 100 in total of the hydroxyl group formed by reaction of the hydroxyl group of (a-1) and the carboxyl group in (a-3), and the epoxy group of the side chain derived from (a-5). It is 5-100 mol with respect to mole, Preferably it is 10-90 mol, More preferably, it is 20-90 mol. The acid value (JIS K 6901) of the copolymer (A-3) obtained can be adjusted to the range of 20-180 mgKOH / g by making the number-of-moles of anhydrous polybasic acid into the range of 5-100 mol with respect to 100 mol of hydroxyl groups.

Reaction of the hydroxyl group of the said copolymer and polybasic acid anhydride (a-6) reacts the unsaturated monobasic acid of (a-3) with the side chain epoxy group derived from (a-5) in the said copolymer, as it is ( a-6) is added in a predetermined amount, and is usually carried out by heating at about 50 to 150 ° C, preferably at 80 to 130 ° C. There is no need to add a new catalyst.

The polybasic acid anhydride of (a-6) in the copolymer (A-3) of the present invention is not particularly limited, and examples thereof include succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, phthalic anhydride, Tetrahydro phthalic anhydride, endomethylene tetrahydro phthalic anhydride, methyltetrahydro phthalic anhydride, hexahydro phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among these, tetrahydro phthalic anhydride and succinic anhydride are preferably used. These may use together 1 type (s) or 2 or more types.

In the photosensitive resin composition of this invention containing the polymer component (A) and photopolymerizable monomer (B) of copolymer (A-1)-(A-3) obtained as mentioned above, a photoinitiator (C) and a solvent (D) can be added.

The photopolymerizable monomer (B) that can be used is not particularly limited as long as it can react with the polymer component (A). For example, Aromatic vinyl monomers, such as styrene, (alpha) -methylstyrene, (alpha)-chloromethyl styrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallyl benzene phosphonate; Polycarboxylic acid monomers such as vinyl acetate and vinyl adipic acid; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethylene glycol Di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylic monomers such as tri (meth) acrylate of meta) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tris (hydroxyethyl) isocyanurate; Triallyl cyanurate and the like. You may use these 1 type, or 2 or more types together.

The addition amount of a photopolymerizable monomer (B) is 10-200 weight part normally with respect to 100 weight part of polymer components (A), Preferably it is 20-150 weight part.

By setting it in the said range, photocurability can be maintained in an appropriate range, and a viscosity can also be adjusted.

As a solvent (D) added to the photosensitive resin composition, if it is an inert solvent which does not react with a polymer component (A) and a photopolymerizable monomer (B), it can be used without a restriction | limiting.

As a solvent (D) which can be used, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, dipropylene glycol mono Methyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate, and the like. Can be mentioned. In these, the propylene glycol monomethyl ether acetate used preferably in the said radical polymerization reaction is used preferably.

The addition amount of a solvent (D) is 30-1000 weight part normally with respect to 100 weight part of polymer components (A), Preferably it is 50-800 weight part. By setting it as the said range, a viscosity can be maintained moderately.

In the photosensitive resin composition of this invention, when photocuring using active light, such as an ultraviolet-ray, as an active energy ray, a photoinitiator (C) is added. Although it does not specifically limit as a photoinitiator (C) which can be used, For example, benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and its alkyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone and 4- (1-t-butyldioxy-1-methylethyl) acetophenone; Anthraquinones such as 2-methyl anthraquinone, 2-amylanthraquinone, 2-t-butyl anthraquinone and 1-chloro anthraquinone; Thioxanthones such as 2,4-dimethyl thioxanthone, 2,4-diisopropyl thioxanthone, and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone and 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone ; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone- One; Acyl phosphine oxides, xanthones, etc. are mentioned. These may use together 1 type (s) or 2 or more types. 0.1-30 weight part is preferable normally with respect to 100 weight part of solid content in the photosensitive resin composition of this invention, More preferably, the compounding quantity of a photoinitiator (C) is 0.5-20 weight part, More preferably, it is 1-10 weight part. . By setting it as 0.1-30 weight part, photocurability can be maintained in a suitable range.

Moreover, the photosensitive resin composition of this invention can contain a well-known coloring agent, an antifoamer, a coupling agent, a leveling agent, etc. as needed.

As said coloring agent, well-known coloring agents, such as an inorganic pigment, an organic pigment, and dye, can be used.

Specific examples of the pigment that can be used include, for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, Yellow pigments such as 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. Pigments; Blue pigments such as C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 16, 60 and the like; Violet pigments such as C.I. pigment violet 1, 19, 23, 29, 32, 36, 38; Green pigments such as C.I. Pigment Green 7, 36; Brown pigments such as C.I. Pigment Brown 23, 25; Pigment 1, 7, Black pigments, such as carbon black, titanium black, iron oxide, etc. are mentioned. These coloring agents are used individually or in combination of 2 or more types, respectively, according to the color of the pixel made into the objective.

Although the compounding quantity of a coloring agent is not specifically limited, Usually, 20-70 weight part is preferable with respect to 100 weight part of solid content in the photosensitive resin composition of this invention, More preferably, it is 25-60 weight part, More preferably, it is 30-50 weight part to be.

In order to improve the dispersibility of a pigment, you may add a well-known dispersing agent further. The dispersant is preferably a polymer dispersant because of its excellent dispersion stability over time. Examples of the polymer dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, aliphatic modified ester dispersants, and the like. . As a specific example of such a dispersing agent, brand names EFKA (made by Efka Chemicals Viv (EFKA) company), Disperbyk (made by Bichemy Co., Ltd.), Desperon (made by Kusumoto Chemical Co., Ltd.), SOLSPERSE (made by Geneca company), etc. are mentioned.

Although the compounding quantity of a dispersing agent is not specifically limited, Usually, 100 weight part or less is preferable with respect to 100 weight part of pigments used, More preferably, it is 1-90 weight part, More preferably, it is 10-70 weight part.

As mentioned above, since the polymer component (A) of this invention has an acid value of 20-180 mgKOH / g, the resists using the photosensitive resin composition containing them can develop using aqueous alkali solution.

The photosensitive resin composition of this invention is apply | coated to a printed wiring board, a glass substrate, an array substrate, for example by the screen printing method, the roll coater method, the curtain coater method, the spray coater method, the spin coater method, etc., and photocured the required part. Thereafter, development is performed by washing the uncured (unexposed) portion with an aqueous alkali solution. As the aqueous alkali solution used for development, aminophenol compounds are also useful in aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate and sodium hydroxide, and amine compounds, but p-phenylenediamine compounds are preferably used. 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N aqueous solutions of -β-methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof.

Low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps and the like are used as light sources used for curing the coated surface by light irradiation.

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited at all by these examples.

In addition, all parts and percentages are based on weight unless otherwise specified. The molecular weight of a copolymer is the weight average molecular weight (Mw) of polystyrene conversion measured by GPC (gel permeation chromatography).

Synthesis Example 1

Into a flask equipped with a stirring device, a dropping lot, a condenser, a thermometer, and a gas introduction tube, 700 g of propylene glycol monomethyl ether acetate was added as a solvent, and the mixture was stirred while nitrogen-substituted and heated to 120 ° C. Next, 53.2 g of tricyclodecanyl methacrylate (a-2), 19.3 g of glycerol monoacrylate (a-1), 165.4 g of vinyltoluene (a-4), and 56.1 g of methacrylic acid (a-3) To the monomer mixture consisting of 6.0 g of t-butylperoxy-2-ethylhexanoate was added. This was dripped at the flask over 2 hours from the dropping lot, and also it stirred at 120 degreeC for 2 hours, and the solution of the copolymer (A-1) -1 (photosensitive resin 1) of 122.0 mgKOH / g of solid content acid value and the weight average molecular weight 29800 was carried out. Got it.

Synthesis Example 2

Into the flask as in Synthesis Example 1, 600 g of propylene glycol monomethyl ether acetate was added as a solvent, stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. Next, 73.4 g of cyclohexyl methacrylate (a-2), 69.9 g of glycerol monoacrylate (a-1), 171.9 g of vinyltoluene (a-4), and 50.1 g of methacrylic acid (a-3) 34.7g of t-butylperoxy-2-ethylhexanoate was added to the monomer mixture. This was dripped at the flask over 2 hours from the dropping lot, and also it stirred at 120 degreeC for 2 hours, and the solution of the copolymer (A-1) -2 (photosensitive resin 2) of 81.7 mgKOH / g of solid content acid value and the weight average molecular weight 9500 was carried out. Got it.

Synthesis Example 3

Into the flask as in Synthesis Example 1, 700 g of propylene glycol monomethyl ether acetate was added as a solvent, stirred while replacing with nitrogen, and heated to 120 ° C. Next, 45.9 g of tricyclodecanyl methacrylate (a-2), 33.4 g of glycerol monoacrylate (a-1), 96.0 g of vinyltoluene (a-4), and 73.6 g of methacrylic acid (a-3) To the monomer mixture consisting of, 5.0 g of t-butylperoxy-2-ethylhexanoate was added. This was dripped at the flask over 2 hours from the dropping lot, and also it stirred at 120 degreeC for 2 hours, and obtained the solution of a copolymer. Subsequently, the flask was replaced with air, 44.4 g of glycidyl methacrylate (a-5), 0.8 g of triphenylphosphine and 0.8 g of methylhydroquinone were charged into the copolymer solution, and the reaction was continued at 120 ° C. The solution of the copolymer (A-2) -1 (photosensitive resin 3) of 101.4 mgKOH / g of solid content acid value and the weight average molecular weight 30500 was obtained.

Synthesis Example 4

Into the flask as in Synthesis Example 1, 600 g of propylene glycol monomethyl ether acetate was added as a solvent, and the mixture was stirred while replacing with nitrogen to raise the temperature to 120 ° C. Next, 40.5 g of cyclohexyl methacrylate (a-2), 38.6 g of glycerol monoacrylate (a-1), 93.3 g of methacrylic acid (a-3), and 148.5 g of benzyl methacrylate (a-4) To the monomer mixture consisting of, 25.3 g of t-butylperoxy-2-ethylhexanoate was added. This was dripped at the flask over 2 hours from the dropping lot, and also it stirred at 120 degreeC for 2 hours, and obtained the copolymer solution. Subsequently, the flask was replaced with air, 51.4 g of glycidyl methacrylate (a-5), 1.2 g of triphenylphosphine and 1.2 g of methylhydroquinone were added to the copolymer solution, and the reaction was continued at 120 ° C. To obtain a solution of Copolymer (A-2) -2 (Photosensitive Resin 4) having a solid acid value of 101.4 mgKOH / g and a weight average molecular weight of 10500.

Synthesis Example 5

Into the flask as in Synthesis Example 1, 700 g of propylene glycol monomethyl ether acetate was added as a solvent, stirred while replacing with nitrogen, and heated to 120 ° C. Next, 27.9 g of tricyclodecanyl methacrylate (a-2), 20.3 g of glycerol monoacrylate (a-1), 99.2 g of glycidyl methacrylate (a-5), and styrene monomer (a-4) ) 33.0 g was added, and 3.7 g of t-butylperoxy-2-ethylhexanoate was added. This was added to the flask over 2 hours from the dropping lot, and also it stirred at 120 degreeC for 2 hours, and obtained the copolymer (1) solution. Subsequently, the flask was replaced with air, and 48.8 g of acrylic acid (a-3), 0.8 g of triphenylphosphine and 0.8 g of methylhydroquinone were charged into the copolymer (1) solution, and the reaction was continued at 120 ° C. When the acid value of solid content became 0.8 mgKOH / g, reaction was complete | finished and the copolymer (1a) solution was obtained. Subsequently, 65.6 g of tetrahydro phthalic anhydride (a-6) was added, and it was made to react at 115 degreeC for 2 hours, and the copolymer (A-3) -1 (photosensitive resin 5) of 80.7 mgKOH / g of solid content acid value and the weight average molecular weight 30800. A solution of was obtained.

Synthesis Example 6

Into the flask as in Synthesis Example 1, 600 g of propylene glycol monomethyl ether acetate was added as a solvent, stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. Next, 36.3 g of tricyclodecanyl methacrylate (a-2), 55.4 g of cyclohexyl methacrylate (a-2), 26.4 g of glycerol monoacrylate (a-1), glycidyl methacrylate ( a-5) 20.5 g of t-butylperoxy-2-ethylhexanoate was added to the monomer mixture consisting of 117.1 g and 19.5 g of vinyltoluene (a-4). This was added to the flask over 2 hours from the dropping lot, and also it stirred at 120 degreeC for 2 hours, and obtained the copolymer (2) solution. Subsequently, the flask was replaced with air, 57.6 g of acrylic acid (a-3), 1.0 g of triphenylphosphine and 1.0 g of methylhydroquinone were added thereto, and the reaction was continued at 120 ° C to give an acid value of solid content of 0.8 mgKOH / g. When it became reaction, reaction was complete | finished and the copolymer (2a) solution was obtained. Subsequently, 65.2 g of tetrahydro phthalic anhydride (a-6) was added and reacted at 115 ° C for 2 hours to give a solid acid value of 60.2 mgKOH / g and a weight average molecular weight of 9400 of Copolymer (A-3) -2 (photosensitive resin 6). A solution was obtained.

Comparative Synthesis Example 1

Into the flask as in Synthesis Example 1, 600 g of propylene glycol monomethyl ether acetate was added as a solvent, stirred while replacing with nitrogen, and heated to 120 ° C. Next, t-butylperoxy-2-ethylhexahexane was added to a monomer mixture consisting of 74.4 g of glycerol monoacrylate (a-1), 241.8 g of vinyltoluene (a-4) and 50.7 g of methacrylic acid (a-3). 32.9 g of noate were added. This was dripped at the flask over 2 hours from the dropping lot, and also it stirred at 120 degreeC for 2 hours, and obtained the solution of the comparative photosensitive resin 1 of 82.7 mgKOH / g of solid content acid value, and the weight average molecular weight 10200.

Comparative Synthesis Example 2

Into the flask as in Synthesis Example 1, 600 g of propylene glycol monomethyl ether acetate was added as a solvent, stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. Next, t-butylperoxy-2-ethyl was added to a monomer mixture consisting of 190.7 g of cyclohexyl methacrylate (a-2), 130.6 g of vinyltoluene (a-4) and 51.2 g of methacrylic acid (a-3). 27.5 g of hexanoate were added. This was dripped at the flask over 2 hours from the dropping lot, and also it stirred and reacted at 120 degreeC for 2 hours, and obtained the solution of the comparative photosensitive resin 2 of solid content acid value 83.6 mgKOH / g and the weight average molecular weight 9200.

Comparative Synthesis Example 3

Into the flask as in Synthesis Example 1, 700 g of propylene glycol monomethyl ether acetate was added as a solvent, stirred while replacing with nitrogen, and heated to 120 ° C. Next, 46.9 g of tricyclodecanyl methacrylate (a-2), 27.7 g of 2-hydroxyethyl methacrylate (a-4), 98.1 g of vinyltoluene (a-4), and methacrylic acid (a-) 3) 5.1 g of t-butylperoxy-2-ethylhexanoate was added to the monomer mixture consisting of 75.1 g. This was dripped at the flask over 2 hours from the dropping lot, and also it stirred at 120 degreeC for 2 hours, and obtained the solution of the copolymer. Subsequently, the flask was replaced with air, 45.4 g of glycidyl methacrylate (a-5), 0.9 g of triphenylphosphine and 0.9 g of methylhydroquinone were charged into the copolymer solution, and the reaction was continued at 120 ° C. The solution of the comparative photosensitive resin 3 of 103.6 mgKOH / g of solid content acid value and the weight average molecular weight 29800 was obtained.

Comparative Synthesis Example 4

Into the flask as in Synthesis Example 1, 650 g of propylene glycol monomethyl ether acetate was added as a solvent, stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. Next, t-butylpere was added to a monomer mixture consisting of 128.5 g of tricyclodecanyl methacrylate (a-2), 68.6 g of methacrylic acid (a-3) and 99.4 g of benzyl methacrylate (a-4). 10.1 g of oxy-2-ethylhexanoate was added. This was dripped at the flask over 2 hours from the dropping lot, and also it stirred and reacted at 120 degreeC for 2 hours, and obtained the copolymer solution. Subsequently, the flask was replaced with air, 41.5 g of glycidyl methacrylate (a-5), 1.0 g of triphenylphosphine and 1.0 g of methylhydroquinone were added to the copolymer solution, and the reaction was carried out at 120 ° C. Then, the solution of comparative photosensitive resin 4 of 81.1 mgKOH / g of solid content acid value and the weight average molecular weight 20800 was obtained.

Comparative Synthesis Example 5

Into the flask as in Synthesis Example 1, 600 g of propylene glycol monomethyl ether acetate was added as a solvent, stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. Next, t-butyl in a monomer mixture consisting of 27.1 g of glycerol monoacrylate (a-1), 144.2 g of glycidyl methacrylate (a-5) and 72.1 g of n-butyl methacrylate (a-4) 19.5 g of peroxy-2-ethylhexanoate were added. This was dripped at the flask over 2 hours from the dropping lot, and also it stirred and reacted at 120 degreeC for 2 hours, and obtained the copolymer solution. Subsequently, the flask was replaced with air, 70.9 g of acrylic acid (a-3), 1.0 g of triphenylphosphine and 1.0 g of methylhydroquinone were added to the solution of the copolymer, and the reaction was continued at 120 ° C to obtain a solid content. When the acid value became 0.8 mgKOH / g, the reaction was terminated to obtain a copolymer solution. Subsequently, 64.3 g of tetrahydro phthalic anhydride (a-6) was added and reacted at 115 degreeC for 2 hours, and the solution of the comparative photosensitive resin 5 of 59.3 mgKOH / g of solid content acid value and the weight average molecular weight 9800 was obtained.

Comparative Synthesis Example 6

Into the flask as in Synthesis Example 1, 700 g of propylene glycol monomethyl ether acetate was added as a solvent, stirred while replacing with nitrogen, and heated to 120 ° C. Next, t- was added to a monomer mixture consisting of 56.9 g of cyclohexyl methacrylate (a-2), 96.2 g of glycidyl methacrylate (a-5), and 16.0 g of n-butyl methacrylate (a-4). 5.1 g of butylperoxy-2-ethylhexanoate were added. This was dripped at the flask over 2 hours from the dropping lot, and also it stirred and reacted at 120 degreeC for 2 hours, and obtained the solution of the copolymer. Subsequently, the flask was replaced with air, and 47.3 g of acrylic acid (a-3), 0.7 g of triphenylphosphine and 0.7 g of methylhydroquinone were added to the copolymer solution, and the reaction was continued at 120 ° C to give an acid value of solid content. When the reaction amount was 0.8 mgKOH / g, the reaction was terminated to obtain a solution of the copolymer. Subsequently, 77.2 g of tetrahydro phthalic anhydride (a-6) was added and reacted at 115 degreeC for 2 hours, and the solution of the comparative photosensitive resin 6 of 95.0 mgKOH / g of solid content acid value and the weight average molecular weight 31000 was obtained.

Examples 1-6, Comparative Examples 1-6

As Examples 1-6, each solution of the photosensitive resins 1-6 obtained by the synthesis examples 1-6 was used for each solution of the comparative photosensitive resins 1-6 obtained by the comparative synthesis examples 1-6 as the comparative examples 1-6. . The wetted photosensitive resin composition prepared by adding 30 parts of pentaerythritol tetraacrylate and 4 parts of 2,2-dimethoxy-2-phenylacetophenone as a photopolymerization initiator to 100 parts of solid content of each photosensitive resin solution was wetted on a glass substrate with an applicator. After coating at 10 μm, the low boiling point was volatilized in a warm air dryer at 100 ° C., an ultra-high pressure mercury lamp manufactured by Oak Manufacturing Co., Ltd. Then, alkali image development was performed.

<Preparation of Green Pigment Dispersion 1>

7.58 parts by weight of CI Pigment Green 36, 7.58 parts by weight of photosensitive resin 2 obtained in Synthesis Example 2, 28.54 parts by weight of propylene glycol monomethyl ether acetate, and a dispersant in a SUS container filled with 180 parts by weight of zirconia beads having a diameter of 0.5 mm. 6.31 parts by weight of Disperbyk-161 manufactured by BIC Chemistry Co., Ltd. was added and dispersed for 6 hours in a paint shaker to obtain a green pigment dispersion 1.

<Preparation of Green Pigment Dispersion 2>

7.58 parts by weight of CI Pigment Green 36, 7.58 parts by weight of Comparative Photosensitive Resin 2 obtained in Comparative Synthesis Example 2, 28.54 parts by weight of propylene glycol monomethyl ether acetate in an SUS container filled with 180 parts by weight of zirconia beads having a diameter of 0.5 mm, and 6.31 parts by weight of a dispersant (Disperbyk-161 manufactured by BIC Chem) was added and dispersed for 6 hours in a paint shaker to obtain a green pigment dispersion (2).

<Preparation of green photosensitive resin composition 1>

50 parts by weight of the obtained green pigment dispersion 1, 20.8 parts by weight of the photosensitive resin 3 obtained in Synthesis Example 3, 6.25 parts by weight of dipentaerythritol hexaacrylate, 2.5 to Irgacure 907 (manufactured by Chiba Specialty Chemicals, Inc.) 31.1 weight part of weight part and propylene glycol monomethyl ether acetate were mixed, and the green photosensitive resin composition 1 was obtained.

<Preparation of green photosensitive resin composition 2>

50 parts by weight of the green pigment dispersion 2 obtained above, 20.8 parts by weight of the comparative photosensitive resin 4 obtained in Comparative Synthesis Example 4, 6.25 parts by weight of dipentaerythritol hexaacrylate, Irgacure 907 (manufactured by Chiba Specialty Chemicals, Inc.) 2.5 parts by weight of propylene glycol monomethyl ether acetate and 31.1 parts by weight were mixed to obtain a green photosensitive resin composition 2.

Example 7, Comparative Example 7

Applying green photosensitive resin composition 1 as Example 7 and green photosensitive resin composition 2 as comparative example 7, respectively, on a glass substrate with an applicator so that thickness may be set to 2 micrometers, and a low boiling point thing is applied in a 100 degreeC warm air dryer. After the volatilization, an ultra-high pressure mercury lamp manufactured by Oak Manufacturing Co., Ltd. was used and exposed to 150 mJ / cm 2 through a mask as necessary to obtain a cured coating film having a thickness of 2 m, followed by alkali development.

(1) heat resistance test

Each cured coating film obtained in Examples 1-7 and Comparative Examples 1-7 was cut out and thermogravimetric analysis (TGA) was performed. The sample cut out was heated to 220 degreeC, and the weight change rate when hold | maintained for 2 hours was measured.

(2) heat discoloration test

The coating film formed on the glass substrate was left to stand in a 230 degreeC dryer for 1 hour, the coloring of the coating film before and behind heat processing was compared with the color difference meter, and the following references | standards evaluated.

○: ΔE * ab is 0.3 or less

X: ΔE * ab is greater than 0.3

(3) Transparency

The coating film formed on the glass substrate was left to stand in a 230 degreeC dryer for 1 hour, the transmittance | permeability in 400 nm of the coating film before and behind heat processing was measured with the spectrophotometer, and the following references | standards evaluated.

○: the rate of change of transmittance is 1% or less

×: change rate of transmittance is more than 1%

(4) Adhesion

A cross-cut adhesion test was conducted in accordance with JIS K 5400 using a cured coating film, and the peeling states of 100 checkerboard scales were visually observed and evaluated according to the following criteria.

(Circle): Peeling was not confirmed at all.

X: Peeling is confirmed by 10% or more of the whole.

(5) alkali developability

The cured coating film exposed through the mask was spray-developed at 23 degreeC using 0.1% sodium carbonate aqueous solution, the presence or absence of the coating film after water washing was observed, and the following references | standards evaluated.

(Circle): After development time 70 second, there is no coating with eyes

×: After a developing time of 70 seconds, there is a coating film with eyes.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Heat resistance (%) -0.6 -0.8 -0.9 -2.8 Discoloration resistance (ΔE * ab) ○ ○ × ○ Transparency (400nm%) ○ ○ × ○ Adhesiveness ○ ○ ○ × Alkali developability ○ ○ × ×

Example 3 Example 4 Comparative Example 3 Comparative Example 4 Heat resistance (%) -0.9 -1.2 -1.0 -2.1 Discoloration resistance (ΔE * ab) ○ ○ ○ ○ Transparency (400nm%) ○ ○ ○ ○ Adhesiveness ○ ○ × × Alkali developability ○ ○ × ×

Example 5 Example 6 Comparative Example 5 Comparative Example 6 Heat resistance (%) -0.4 -0.8 -3.8 -2.9 Discoloration resistance (ΔE * ab) ○ ○ × ○ Transparency (400nm%) ○ ○ × ○ Adhesiveness ○ ○ ○ × Alkali developability ○ ○ ○ ×

Example 7 Comparative Example 7 Heat resistance (%) -1.0 -2.3 Discoloration resistance (ΔE * ab) ○ ○ Transparency (400nm%) ○ ○ Adhesiveness ○ × Alkali developability ○ ×

In Tables 1-4, in an Example, there is little weight loss at the time of a heating, heat discoloration, deterioration of transparency, peeling of a cured coating film is not recognized, and also it does not impair alkali developability.

Since the cured coating film formed from the photosensitive resin composition of this invention is excellent in heat resistance and adhesiveness with respect to a glass substrate and a semiconductor substrate, and has alkali developability, it is very useful in various resist fields.

Claims (8)

A photosensitive resin composition comprising a polymer component (A) and a photopolymerizable monomer (B), wherein the polymer component (A) has a polymerizable monomer (a-1) having two or more hydroxyl groups in a molecule and 6 to 20 carbon atoms in the molecule. It is a polymer containing the monomer component which has a polymerizable monomer (a-2) which has an alicyclic skeleton which may have a crosslinked structure of the photosensitive resin composition characterized by the above-mentioned. The method according to claim 1, The photosensitive resin composition whose acid value of a polymer component (A) is 20-180 mgKOH / g. The method according to claim 1, The photosensitive resin composition whose weight average molecular weight of a polymer component (A) is 5000-80000. The method according to claim 1, The said polymer component (A) has a polymerizable monomer (a-1) which has a 2 or more hydroxyl group in a molecule, and the polymerizable monomer (a-2) which has an alicyclic skeleton which may have a C6-C20 crosslinked structure in a molecule | numerator. And an air formed by copolymerizing an unsaturated monobasic acid (a-3) and radically polymerizable compounds (a-4) other than (a-1), (a-2) and (a-3) copolymerizable with them. Photosensitive resin composition which is coalescence (A-1). The method according to claim 1, The said polymer component (A) has a polymerizable monomer (a-1) which has a 2 or more hydroxyl group in a molecule, and the polymerizable monomer (a-2) which has an alicyclic skeleton which may have a C6-C20 crosslinked structure in a molecule | numerator. Copolymerized with an unsaturated monobasic acid (a-3) and radical polymerizable compounds (a-4) other than (a-1), (a-2) and (a-3) which can be copolymerized with them. The photosensitive resin composition which is a copolymer (A-2) formed by making the carboxyl group in a copolymer react with the radically polymerizable compound (a-5) which has an epoxy group. The method according to claim 1, The said polymer component (A) has a polymerizable monomer (a-1) which has a 2 or more hydroxyl group in a molecule, and the polymerizable monomer (a-2) which has an alicyclic skeleton which may have a C6-C20 crosslinked structure in a molecule | numerator. And a radical polymerizable compound (a-4) other than (a-1), (a-2) and (a-5) which can be copolymerized with the radical polymerizable compound (a-5) having an epoxy group. The photosensitive resin composition which is a copolymer (A-3) formed by making an unsaturated monobasic acid (a-3) react with the epoxy group in the obtained copolymer, and then making polybasic acid anhydride (a-6) react with a hydroxyl group. The method according to claim 1, The photosensitive resin composition which further contains a photoinitiator (C) and a solvent (D). The method of claim 1 or claim 7, The photosensitive resin composition which further contains a coloring agent.