JPH0392860A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive resin composition high in sensitivity by composing it essentially of a polymer having structural units each derived from an acryloyl group having an aryl group substituted by at least one electron donative group at the beta position and structural units each derived from an acryloyl group having an aryl group substituted by at least one electron attractive group at the beta position. CONSTITUTION:The polymer is composed essentially of the structural units each derived from the acryloyl group having an aryl group substituted by at least one electron donative group at the beta position and structural units each derived from the acryloyl group having the electron attractive group at the betaposition. The 'the acryloyl group having the aryl group at the beta position' is represented by formula I R<1> H or a monovalent organic group and R<2> is an aryl group, is thus permitting the photosensitive resin composition high in sensitivity to be obtained.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a highly sensitive photosensitive resin containing a polymer having a photodimerizable group, which can be used in image forming materials such as LSI elements and printing plates. Regarding kumiimono.

[Prior Art] Photocrosslinkable materials that are crosslinked by a cocycloaddition reaction are well known, and these are used in image forming materials such as LSI devices and printing plates. Among these photocrosslinkable materials, photosensitive resins having a cinnamoyl group, a cinnamylidene acetate group, a chalcone group, etc. in the side chain or main chain, which have a photodimerizable unsaturated double bond adjacent to an aromatic nucleus, are useful and have a practical use. There are some that have been converted. However, they generally have lower sensitivity than photopolymerizable photosensitive resins, etc., and various improvements have been attempted to increase sensitivity.

Since many of the above-mentioned photosensitive resins having photodimerizable unsaturated double bonds have an absorption maximum around 300 nm,
Conventionally, means for increasing sensitivity have mainly been directed to the search for sensitizers. Special Publication No. 51-46697, Special Publication No. 52
-41054, JP 5-5-3-3-6-9-9, JP-A-57-24935, JP-A-60-93427
Descriptions of useful sensitizers can be found in the above publications. However, the effects are still not sufficient.

On the other hand, as other means for increasing sensitivity, for example, there are methods that utilize interaction between photosensitive groups. Japanese Patent Publication No. 55-1189
No. 11 describes a method of blending a polymer having an electron-donating group and an electron-withdrawing group on each phenyl group of a cinnamoyl residue. This is because the interaction between the electron-donating group and the electron-withdrawing group increases the reactivity of the photodimerizable unsaturated double bond on the cinnamoyl residue and further promotes the reaction between different polymer chains. This method takes advantage of the fact that crosslinking efficiency increases. However, since it is a blend of two or more types of polymers, compatibility between the polymers may be a problem, and the effect of increasing sensitivity was not sufficient.

[Problem that the invention seeks to solve]

Therefore, an object of the present invention is to provide a photosensitive resin composition with higher sensitivity, which contains a photodimerizable polymer having an unsaturated double bond.

[Means for solving problems]

The present inventor has arrived at the present invention as a result of extensive research in order to achieve the object. That is, the present invention provides (A) an acryloyl group having an aryl group substituted with one or more electron-donating groups at the β-position, and (B) an aryl group substituted with one or more electron-withdrawing groups in the β-position. The present invention relates to a photosensitive resin composition whose main component is a polymer containing an acryloyl group in both positions as a constituent unit. here,
"Acryloyl group having an aryl group at the β position" means a group represented by the following general formula (I).

σ O (R' is a hydrogen atom or a monovalent organic group, R2 is an aryl group) A typical example of the polymer is a polymer containing both the following general formula (II) and general formula (IIr) as constituent units. Can be mentioned.

(R' is a hydrogen atom or a methyl group, R4 is a divalent organic group or a simple bond, RS is a hydrogen atom or an electron donating group, Rs is an aryl group substituted with one or more electron donating groups) R7 j l O (III) (R' is a hydrogen atom or a methyl group, R8 is a divalent organic group or a simple bond, Rg is a hydrogen atom or an electron-withdrawing group, R'' is substituted with one or more electron-withdrawing groups) (aryl group) The polymer containing both the above general formula (II) and general formula (IllF) as constituent units can be obtained by a polymerization method or a polymer reaction method.

Synthesis by polymerization method is general formula (IV) R3 l 0 (■) (R''~R@ are the same as defined previously.

) and general formula (V) R7 C CH. -C R'11 (R'') 10 -C -C -C H -R'
01 0 (V) (R' to Rl0 are the same as defined previously.

) can be achieved by allowing the monomers represented by the formula to coexist and reacting in the presence of a suitable polymerization initiator.

The monomer of general formula (IV) may be a monomer having an electron-donating group-substituted cinnamoyl residue in the molecule. Therefore, R4 of the general formula (IV) simply combines the cinnamoyl residue and the polymerizable group. can be arbitrarily selected from those that can be combined with. Examples of R4 include a simple bond, a hydrocarbon group which may have a substituent, and a hydrocarbon group containing an ether group, an ester group, an amide group, and the like.

Similarly, since the monomer of general formula (V) may be a monomer having a cinnamoyl residue substituted with an electron-withdrawing group in the molecule, Ra of general formula (IV) can also be polymerized with this cinnamoyl residue. It can be arbitrarily selected from those that can play the role of bonding with a functional group.

Monomers of general formula (IV) and general formula (V) are synthesized by various methods. As a representative example, the
As described in Publication No. 22 etc., it has a hydroxy group (
One method involves the reaction of meth)acrylate with substituted cinnamoyl halide.

As a (meth)acrylate having a hydroxy group,
Hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate,
Examples include polypropylene glycol mono(meth)acrylate.

Examples of substituted cinnamoyl halides are 4-dimethylaminocinnamoyl chloride, 4-diethylaminocinnamoyl chloride, 4-dimethylaminocinnamoyl chloride, 4-dimethylaminocinnamoyl chloride, and 4-dimethylaminocinnamoyl chloride.
-methoxycinnamoyl chloride, 3,4-dimethoxycinnamoyl chloride, 2,4-dimethoxycinnamoyl chloride, 4,-methylcinnamoyl chloride and the corresponding bromides. Examples of substituted electron-withdrawing groups include 4-cyanocinnamoyl chloride,
4-Nitrocinnamoyl chloride, 3-nitrocinnamoyl chloride, 2,4-dinitrocinnamoyl chloride, 4-trifluoromethylcinnamoyl chloride, 4-
These include acetylcinnamoyl chloride, 4-chlorocinnamoyl chloride, 4,α-dicyanocinnamoyl chloride and the corresponding bromides.

The monomer obtained by the above reaction can also be obtained by a dehydration reaction of a (meth)acrylate having a hydroxy group and a substituted cinnamic acid.

In addition, reactions between epoxy group-containing addition polymerizable monomers such as glycidyl (meth)acrylate and substituted cinnamic acids,
The desired monomer can also be obtained by reacting a halogenated alkyl group-containing addition polymerizable monomer typified by chloromethylstyrene with a substituted cinnamic acid alkali salt.

The monomers of general formula (IV) and general formula (V) may be copolymerized with other copolymerizable addition polymerizable monomers. Typical monomers include methacrylic acid, methyl methacrylate, ethyl methacrylate, probyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, and acrylic. Acid, methyl acrylate, ethyl acrylate, probyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, acrylonitrile, styrene, α-methylstyrene, vinyltoluene , acrylamide, methacrylamide, vinyl methyl ketone, vinyl propyl ketone, vinyl methyl alcohol, vinyl ethyl ether, vinyl hexyl ether, vinyl acetate, and the like.

The polymer containing both the above general formula (n) and general formula (I[I) as constituent units can also be obtained by a polymer reaction method. A typical synthesis method involves adding the aforementioned electron-donating group-substituted cinnamoyl halide and electron-withdrawing group-substituted cinnamoyl halide to a polymer having an alcoholic hydroxyl group, such as polyvinyl alcohol or poly[2-hydroxyethyl (meth)acrylate]. One example is a method of reacting moyl halide in stages. Other examples include reactions between epoxy group-containing polymers such as polyglycidyl (meth)acrylate and substituted cinnamic acids, and reactions between halogenated alkyl group-containing polymers such as polychloromethylstyrene and substituted cinnamic acid alkali salts.

The number average molecular weight of the polymer synthesized as above is s
, ooo to 200,000.

If the molecular weight is higher than this range, it will be difficult to dissolve in solvents and will interfere with various uses, and if the molecular weight is lower than this range, the strength of the resin after photocrosslinking will be low, making it impractical.

Further, the ratio of (A) structural units and (B) structural units in the polymer is such that the (A)/(B) molar ratio is 20/80 to 80.
The range is preferably /20.

Within this range, interaction occurs between (A) and (B), resulting in higher photoreactivity than a polymer consisting only of each unit.

Although the polymer has increased photoreactivity as it is due to the interaction between the (A) structural unit and the (B) structural unit, its function can be further enhanced by using a sensitizer.

Sensitizers include benzophenone derivatives, penzanthrone derivatives, quinones, aromatic nitro compounds, naphthothiazoline derivatives, penzothiazoline derivatives, thioxanthones, naphthothiazole derivatives, ketocoumarin compounds,
Examples include penzothiazole derivatives, naphthofuranone compounds, biryllium salts, and thiavirylium salts.

Specifically, Michler's ketone, N,N'-diethylaminobenzophenone, penzanthrone, (3-methyl-1,3-diaza-1,9-benz)anthrone picramide, 5-nitroacenaphthene, 2-chlorothioxanthone, 2- Isoprobylthioxanthone, dimethylthioxanthone, methylthioxanthone-1-ethylcarboxylate, 2-nitrofluorene, 2-penzoylmethylene-3-methylnaphthothiazoline, 2-dibenzoylmethylene-3-methylnaphthothiazoline, 3,3'carbonylrubis( 7-diethylaminocoumarin), 2
, 4.6-4 rifhenylthiapyrylium verchlorate, 2-(varchlorobenzoyl)naphthothiazole and U.S. Pat. No. 4,147,552, No. 4,062,6
Examples include sensitizers disclosed in Japanese Patent No. 86 and No. 4,116,466. The appropriate amount of these sensitizers added is about 0.5 to about 20% by weight, more preferably 1-10% by weight of the total composition.

The photosensitive resin composition of the present invention may further contain additives such as dyes, adhesion promoters, and plasticizers, if necessary.

Examples of dyes are brilliant green, eosin, ethyl violet, erythrosin B, methyl green, crystal violet, page sokfuchsin, phenolphthalein, methyl orange, rose methyl red, congo red, methyl violet, malachite green, etc.

Examples of adhesion promoters include penzimidazole, compounds, 2-mercaptobenzthiazole, 2-mercaptobenzimidazole, and other compounds described in JP-A-53-702.

Examples of plasticizers include phthalic acid esters such as dibutyl phthalate and diheptyl phthalate; glycol esters such as triethylene glycol diacetate and tetraethylene glycol diacetate.

The photosensitive resin composition of the present invention is dissolved in an organic solvent such as methyl ethyl ketone, cyclohexanone, acetone, tetrahydrofuran, dimethyl formamide, dimethyl sulfoxide, ethyl cellosolve, dichloroethane, etc. - Casting onto the surface of plastic base such as
A film can be formed by forming a uniform layer by means such as spraying or coating, and then drying it. After performing image forming exposure on the photosensitive resin film obtained in this way,
A clear relief image can be obtained by performing a development process using the above-mentioned organic solvent.

The photosensitive resin composition of the present invention has high photoreactivity and is more sensitive than compositions made of homopolymers.

In addition, at first glance, it seems that intramolecular reactions take precedence because the same polymer chain contains electron-donating units and electron-accepting units, but contrary to expectations, the sensitivity is higher when a mixture of two or more homopolymers is used. Moreover, it is easy to prepare a solution without worrying about compatibility, so it is very useful for applications such as photoresists and printing plates.

〔Example〕

Below, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these.

Example 1 10 parts by weight of 2-(4-diethylaminocinnamoyloxy)ethyl methacrylate, 10 parts by weight of 2-(4-trifluoromethylcinnamoyloxy)ethyl methacrylate, 80 parts by weight of tetrahydrofuran, and 2,2'-azobis (2.4-Dimethylvaleronitrile) 0.02 parts by weight was mixed, and after purging with nitrogen gas for 10 minutes, 62 parts by weight of
It was immersed in a constant temperature bath at ℃ for 8 hours. By dropping the reaction product into methanol, a copolymer was obtained as a yellow powdery solid. The number average molecular weight was determined to be 27,500 by molecular weight measurement using GPC.

10 parts by weight of this polymer was dissolved in 90 parts by weight of cyclohexanone, and the solution was coated on an aluminum plate that had been subjected to a hydrophilic treatment using a rotary coater and dried. A gray scale whose density changes in increments of 0.15 per l step (Fuji Step Guide P, manufactured by Fuji Photo Film Co., Ltd.) was overlaid on the resin film thus obtained, and a 2kW ultra-high pressure mercury was used as a light source. Lamp (manufactured by Oak Seisakusho Co., Ltd. "Jet Printer J"
P-2000EXJ) was used for ioo count exposure. This sample was developed and stained with cyclohexanone according to a conventional method, and the number of insolubilization stages was determined. The results are shown in the table. The larger the number, the higher the sensitivity.

Example 2 10.7 parts by weight of 2-(4-diethylaminocinnamoyloxy)ethyl methacrylate, 9.3 parts by weight of 2-(4-cyanocinnamoyloxy)ethyl methacrylate,
80 parts by weight of tetrahydrofuran and 0.02 parts by weight of 2,2'-azobis(2,4-dimethylvalenitrile) were mixed and reacted under the same conditions as in Example 1 to obtain a yellow powdery solid. The number average molecular weight was determined to be 33,100 by molecular weight measurement using GPC. Example 1 Using this polymer
Samples were prepared and evaluated in the same manner as described above. The results are shown in the table.

Comparative Example 1 2-(4-diethylaminocinnamoyloxy)ethyl methacrylate was polymerized under the same conditions as in Example 1 to synthesize a homopolymer. The number average molecular weight is 14 by GPC.
I was asked for 500. Using this polymer, samples were prepared and evaluated in the same manner as in Example 1. The results are shown in the table.

Comparative Example 2 2-(4-trifluoromethylcinnamoyloxy)ethyl methacrylate was polymerized under the same conditions as in Example 1 to synthesize a homopolymer. The number average molecular weight was determined by GPC to be 2.
5600 was requested. Using this polymer, samples were prepared and evaluated in the same manner as in Example 1. The results are shown in the table.

Comparative Example 3 2-(4-cyanocinnamoyloxy)ethyl methacrylate was polymerized under the same conditions as in Example 1 to synthesize a homopolymer. The number average molecular weight was determined to be 23,200 by GPC. Using this polymer, samples were prepared and evaluated in the same manner as in Example 1.

The results are shown in the table.

Comparative Example 4 5 parts by weight of each of the homopolymers synthesized in Comparative Examples 1 and 2 and 90 parts by weight of cyclohexanone were mixed to prepare a solution. Using this, samples were prepared and evaluated in the same manner as in Example 1.

The results are shown in the table.

Comparative Example 5 5.4 parts by weight of the homopolymer synthesized in Comparative Example 1, 4.6 parts by weight of the homopolymer synthesized in Comparative Example 3, and 90 parts by weight of cyclohexanone were mixed to prepare a solution. Using this, samples were prepared and evaluated in the same manner as in Example 1. The results are shown in the table.

Table [Effects of the Invention] The photosensitive resin composition of the present invention has high photoreactivity and high sensitivity, and is also more sensitive than a mixture of two or more homopolymers, and does not have to worry about compatibility. Since there is no need to do this, it is very useful for applications such as photoresists and printing plates.

Claims (1)

[Claims] (A) an acryloyl group having an aryl group substituted with one or more electron-donating groups at the β-position, and (B) an acryloyl group having an aryl group substituted with one or more electron-withdrawing groups at the β-position A photosensitive resin composition whose main component is a polymer containing as a constituent unit