JPS62288603A - Highly sensitive photopolymerizable composition - Google Patents

Abstract

PURPOSE:The titled composition, containing a specific high polymer material, double bond-containing monomer or oligomer and specific photopolymerization initiator system and sensitive to ultraviolet and visible rays and well sensitive particularly to laser beams scanning at a high speed. CONSTITUTION:A composition obtained by blending (A) a film-forming high polymer material consisting of a polymer prepared by reacting a copolymer of styrene and maleic anhydride with an acrylic or methacrylic acid ester monomer, e.g. 2-hydroxyethyl acrylate, with (B) a monomer or oligomer having one or more addition polymerizable C=C bonds in one molecule and (C) an organic coloring matter expressed by formulas I-III [R1 is (substituted) alkyl; R2 is H, CH3, alkoxy, etc.; R3 is R1 or acetyl; R4 is H, halogen, etc.; R5 is R4, (substituted) amino, etc., X is H or halogen; Y is O or S] and N-phenylglycine and/or 2,4,6-substituted-1,3,5-triazine compound as a photopolymerization initiator.

Description

[Detailed Description of the Invention] [Industrial Field of Application J This invention provides a highly sensitive photopolymerizable composition that is sensitive not only to ultraviolet light but also to visible light, and particularly sensitive to laser beams scanned at high speed. Regarding.

[Prior Art] Conventionally, photopolymerizable compositions containing a film-forming polymeric substance, a monomer or oligomer having at least one addition-polymerized carbon-carbon double bond in one molecule, and a photopolymerization initiator have been used. It is widely used as a photosensitive material for manufacturing H11 printing plates, printed circuit boards, semiconductors, etc. In particular, such a photopolymerizable composition is deposited on a transparent support at lO~1
A dry film photoresist formed into a thick layer of approximately 00P is frequently used as a photoresist for producing printed circuit boards.

On the other hand, in recent years, a method of printing a predetermined pattern on a photosensitive material layer using a laser beam has been studied, and has been put into practical use, such as direct laser engraving during printing plate production and laser facsimile. As such photosensitive materials for laser light,
A highly sensitive material is required to be sensitive to a laser beam that is scanned at high speed, and considering that the sensitive wavelength range is, for example, 488 nm for an Ar+ ion laser, a material that is sensitive to visible light is also required. required.

In response to such demands (7), the conventional general photopolymerizable compositions mentioned above are insufficient, and therefore
40 and JP-A No. 60-221403, in place of conventional general photopolymerization initiators such as benzoin alkyl ether and benzyl dimethyl ketal, specific organic dyes or organic dyes and organic peroxides are used. Various attempts have been made to improve the photosensitive characteristics by using special photopolymerization initiators consisting of two-component systems. Through these attempts, considerable results have been obtained in terms of high sensitivity changes and sensitization to visible light, and there are great expectations for their practical application in, for example, PS plates for lithographic printing.

[Problems to be Solved by the Invention] However, the known photopolymerizable composition according to the above-mentioned attempt has good sensitivity characteristics when formed to a thickness of several micrometers, and therefore does not meet the above-mentioned problems. Although it is possible to apply it to PS plates for lithographic printing, etc., when the layer is formed to a thickness of about 10 to 100μ, the sensitivity characteristics deteriorate considerably, and for this reason, it is possible to apply it to PS plates for lithographic printing. There were still difficulties in applying it to dry film photoresists for substrate manufacturing.

An object of the present invention is to provide a highly sensitive photopolymerizable composition that has good sensitivity to ultraviolet light and visible light even when formed into a thick layer as described above, and can also be exposed to laser beams. The purpose is

[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the inventors discovered that while using a specific organic dye and a specific compound together as a photopolymerization initiator, film formation When a specific polymer is used as a polymeric substance, a highly sensitive photopolymerizable composition that has extremely low sensitivity characteristics to ultraviolet light and visible light and is also well sensitive to laser beams can be obtained. They found that even when this layer was formed to a thickness of about 10 to 100 .mu.m, there was no significant deterioration in sensitivity characteristics, leading to the completion of the present invention.

That is, the present invention provides a film-forming polymeric substance containing at least one carbon-carbon double bond capable of addition polymerization in one molecule.
In a photopolymerizable composition containing a monomer or oligomer and a photopolymerization initiator, the polymer substance is a copolymer of styrene and maleic anhydride, and an r-meth)acrylic acid ester monomer having a hydroxyl group in the molecule. consisting of a polymer obtained by reacting the photopolymerization initiator with the following formula +1), flD or surface; [wherein R1 is an alkyl group or a substituted alkyl group, R2
is a hydrogen atom, methyl group, alkoxy group or ami7 group (
R3 is an alkyl group, a substituted alkyl group or an acetyl group, R4 is a hydrogen atom, a halogen atom or a methyl group, R5 is a hydrogen atom, a halogen atom, a methyl group, an alkoxy group or an acetyl group (substituted (contains an amino group), X is a hydrogen atom or a halogen atom, and Y is an oxygen atom or a sulfur atom. Substitution-1
- A highly sensitive photopolymerizable composition characterized by comprising a 3,5-triazine compound.

As described above, the photopolymerizable composition of the present invention is highly sensitive to ultraviolet light and visible light, and is sensitive to laser beams due to the combination of the specific polymer and the specific photoinitiator. This composition has the characteristic of being well sensitive to
Even when a layer is formed as thick as n7'1 degree, there is no significant decrease in sensitivity characteristics, so it has the advantage that it can be applied to dry film photoresists for printed circuit board manufacturing without any problems. In addition, the photopolymerizable composition having the above structure has the property that its dry film dissolves and swells with an aqueous alkaline solution, so it saves resources and requires development work to remove unexposed areas after exposure and curing. It also has the advantage that it can be carried out using the aqueous alkaline solution, which is very advantageous from the standpoint of hygiene.

[Structure and operation of the invention] The film-forming polymeric substance used in this invention is obtained by reacting a copolymer of styrene and maleic anhydride with a (meth)acrylic acid ester monomer having a hydroxyl group in the molecule. The molecule of this polymer contains a (meth)acryloyloxy group derived from the above-mentioned (meth)acrylic acid ester monomer,
The interaction between this and the specific photopolymerization initiator gives very good results in sensitivity characteristics.

The copolymer of styrene and maleic anhydride mentioned above tends to undergo alternating copolymerization in a molar ratio of 1:1, so such an alternating copolymer may also be used. The copolymerization ratio may be changed to some extent by selecting the polymerization conditions. Generally acceptable copolymerization ratios range from 40/60 to 70/30 styrene/maleic anhydride. In addition, in obtaining such a copolymer, other monomers such as acrylic acid, methacrylic acid, butyl acrylate, methyl methacrylate, butyl methacrylate, and acrylonitrile may be used in a proportion of 20 mol% or less of the total monomers. good. That is, the above-mentioned copolymers in the present invention also include copolymers in which the other monomers mentioned above are used as a type of copolymerization monomer. The average molecular weight of these various copolymers is preferably in the range of 10,000 to 300,000.

By reacting this copolymer with a (meth)acrylic acid ester monomer having a hydroxyl group in the molecule to form an ester bond between the acid anhydride group and the hydroxyl group, the polymer as a film-forming polymer substance is produced. get. The above reaction can be carried out, for example, in pyridine using a suitable catalyst such as imidazole at 40 to 80°C for 1 to 24 hours. The reaction rate is preferably such that 30 to 80% of the acid anhydride groups contained in the copolymer participate in the reaction with the (meth)acrylate monomer.

If the reaction rate is too low from the above, it is difficult to obtain good results in terms of improving the sensitivity characteristics, which is the objective of this invention, and conversely, if it is too high, the ability to dissolve or swell with an aqueous alkaline solution after exposure and curing will decrease. Neither is preferable.

Examples of (meth)acrylic acid ester monomers having a hydroxyl group in the molecule used in the above reaction include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
-Hydroxypropyl methacrylate, 1,4-butylene glycol monoacrylate, 1,4-butylene glycol monomethacrylate Those having a molecular weight of 500 or less, such as polyethylene glycol monoacrylate and polyethylene glycol monomethacrylate, are preferred.

One feature of this invention is that the polymer obtained by the above reaction is used as a film-forming polymer substance, but other known film-forming polymers may be used as long as the amount used does not impair the effects of this invention. A polymeric substance such as polymethyl methacrylate, a copolymer of methyl methacrylate and methacrylic acid, polyvinyl alcohol, polyester resin, etc. may be used in combination. The amount of these other polymeric substances used is preferably kept to 20% by weight or less based on the total amount of the polymer.

The monomer or oligomer having at least one addition-polymerized carbon-carbon double bond in one molecule used in the present invention may contain one double bond in one molecule.
There are monoethylenically unsaturated compounds having two or more polyethylenically unsaturated compounds and polyethylenically unsaturated compounds having two or more. Among these, should polyethylenically unsaturated compounds be used alone or in a mixed system with monoethylenically unsaturated compounds?
Particularly preferred.

Examples of monoethylenically unsaturated compounds include acrylic acid or its esters, methacrylic acid or its esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, N-vinyl compounds, styrenes, These include crotonic acid esters.

Specific examples of acrylic esters include propyl acrylate, butyl acrylate, amyl acrylate,
2-ethylhexyl acrylate, octyl acrylate, etc., methacrylic esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, inpropyl methacrylate, etc., and acrylamides include acrylamide, N-alkyl group is methyl group, etc. ethyl group,
Butyl group, isopropyl group, tert-butyl group, 2-
N-alkyl acrylamide, which consists of an ethylhexyl group, etc., is methacrylamide, and N-alkyl methacrylate, whose N-alkyl group is a methyl group, ethyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, etc. There are amides, etc.

In addition, allyl compounds include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, and allyl palmitate, and the vinyl ethers include hexyl vinyl ether, octyl vinyl ether,
Decyl vinyl ether, 2-ethylhexyl vinyl ether, a/l/l-ruvinyl ether, vinyl esters such as tehahynyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate. ,
N-vinyl compounds such as N-vinylpyrrolidone, styrenes include styrene, methylstyrene, chloromethylstyrene, alkoxystyrene, halogenated styrene,
Examples of crotonate esters include styrene benzoate, methyl crotonate, ethyl crotonate, methyl crotonate, hexyl crotonate, and isopropyl crotonate.

Next, examples of polyethylenically unsaturated compounds include polyacrylates and polymethacrylates of polyhydric alcohols. The polyhydric alcohol mentioned above is
Polyethylene glycol, polypropylene oxide, polybutylene oxide, (β-hydroxyethoxy)benzene, glycerin, diglycerin, neopentyl glycol, trimethylolpropane, trimethylolpropane, pentaerythritol, dipentaerythritol,
Sorbitan, sorbitone 1,4-butanediol, 1,2,4-butanetriol, 2-butene 4-
Diol, 2-butyl-2-ethyl-propanediol, 2-butenoto-4-diol, 1,3-propanediol, triethanolamine, decalindiol, 3-
Examples include chlorate 2-propanediol.

In addition, other examples of polyethylenically unsaturated compounds include:
There are acrylate oligomers and methacrylate oligomers having two or more acryloyl groups or methacryloyl groups in the molecule, which are commercially available under the names of oligoester acrylate, oligoester methacrylate, epoxy acrylate, epoxy methacrylate, urethane acrylate, urethane methacrylate, etc.

Such a monomer or oligomer having at least one carbon-carbon double bond capable of addition polymerization (within one molecule) is usually used in an amount of 20 to 200 parts by weight per 100 parts by weight of the film-forming polymeric substance. Particularly preferably, it is used in a proportion of 50 to 150 parts by weight. If this amount is too small or too large, it is difficult to obtain good results in terms of photosensitivity, and if the amount exceeds 3, it is difficult to obtain favorable results in terms of hardness of the cured product.

The photopolymerization initiator used in this invention has the above formula (
1), (II) or (IID) and an organic dye represented by N-phenylglycine and/or 2, 4, 6
-substituted-1,3,5-triazine compound, the former organic dye plays the main function of initiating photopolymerization, and the latter component plays the function of promoting photopolymerization, thereby forming the specific film. This greatly enhances the photosensitive properties of a polymerizable composition containing a formable polymeric substance.

The above organic dyes include formulas (I), (II) or a
A xanthine dye in which Y in ID is an oxygen atom,
There are thioxanthine dyes in which Y is a sulfur atom, and either or both of them can be used.

Also, whether one type of organic dyes represented by formula II), (It) or legs is used, or whether two or three of these organic dyes are used in combination depends on the other constituents of the polymerizable composition. It may be selected as appropriate depending on the type of component.

However, organic dyes represented by formulas (IJ), It is advantageous to use.

In addition, each group in formula (I), (In, (111) will be explained first. Y is an oxygen atom or a sulfur atom as described above, and X is a halogen atom such as a hydrogen atom or a chlorine atom. In addition, R1 in formula CI) is an alkyl group usually having 8 or less carbon atoms, or a substituted alkyl group into which a substituent such as a hydroxyl group or an amine group (including a substituted amine group) is introduced. , R2 is a hydrogen atom, a methyl group, an alkoxy group, or an amine 7 group (including a substituted amine 7 group).

R3 in formula fIJ) and ff1D is the same alkyl group or substituted alkyl group as above, or an acetyl group. Further, R4 is a hydrogen atom, a halogen atom, or a methyl group, and R1 is a hydrogen atom, a halogen atom, a methyl group, an alkoxy group or an amino group (including substituted amine groups such as N-alkyl substitution) having usually 2 or less carbon atoms. ).

Examples of N-phenylglycines used in combination with such organic dyes include N-phenylglycine represented by the following chemical structural formula; Phenylcrinone p-mei
Examples include N-phenylglycine substituted products having a substituent on the benzene ring, such as quin-N-phenylglycine.

In addition, a 2,4,6-substituted-1,3,5-triazine compound is a compound represented by the following chemical structural formula; in which the three groups consisting of R6, R, and R are methyl groups, substituted methyl groups into which a substituent such as a halogen atom has been introduced, or an aryl group with or without a substituent such as a halogen atom or an alkyl group, and are mutually the same but different groups. It may be.

Among such 2,4,6-substituted-1,3,5-triazine compounds, those in which at least one of "6 + R7+ RH consists of a mono-, di-, or trihalogen-substituted methyl group are particularly preferred. An example of the variant is 2,4,6-dostrichloromethyl-i,3
・5-triazine, 2,4,6-tristribromomethyl-1,3,5-triazine, 2,4,6-dolysdichloromethyl-1,3,5-triazine, 2,4,6-dolysdibromo Methyl-1,3,5-triazine, 2-methyl-4,6-pisdrichloromethylto-3,5-triazine, 2-methyl-4,6-pisdribromomethyl-1,3,5-triazine, 2・4,6-Dorischloromethyl-1,3,5-triazine, 2,4,6-Dorisbromomethyl-1,3,5-triazine, 2-phenyl-
4,6-pisdrichloromethyl-1,3,5-triazine, 2-phenyl-4,6-pisdribromomethyl-1
・3,5-triazine, etc.

In this invention, the above-mentioned N-phenylglycines may be used as a component to be used in combination with the above-mentioned organic dye;
- A 4,6-substituted-1,3,5-triazine compound may be used, or both may be used in combination. Furthermore, two or more types of N-phenylglycines may be used as a mixture, and similarly, two or more types of 2,4,6-substituted-1,3,5-triazine compounds may be used as a mixture. can.

The amount of such a two-component photopolymerization initiator to be used is based on 100 parts by weight of a monomer or oligomer having at least one addition-polymerized carbon-carbon double bond in one molecule. 0.1 to 20 parts by weight, particularly preferably 1 to 10 parts by weight, of N-phenylglycines and/or 2,4,6-substituted-1,3,5-triazine compounds 6 (0,1 to 20 parts by weight) Parts by weight, particularly preferably 1 to 10 parts by weight, preferably in such a proportion that the total amount of both is usually 0.5 to 30 parts by weight.

The highly sensitive photopolymerizable composition of the present invention essentially contains the above-mentioned film-forming polymeric substance, a monomer or oligomer having at least one addition-polymerized carbon-carbon double bond in one molecule, and a photopolymerization initiator. In addition to being included as a component, various additives such as a thermal polymerization inhibitor, a coloring agent, an adhesion improver, a filler, and a plasticizer may also be included as optional components.

In use, the highly sensitive photopolymerizable composition of the present invention constructed as described above is prepared by uniformly dissolving and mixing the composition in an appropriate organic solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethinoacetate, butyl acetate, dioxane, etc. It is said that

This solution is directly coated and dried on a substrate to be patterned, such as a copper-clad laminate, or once coated and dried on a transparent support made of plastic or the like to form a dry film photoresist, and then applied to the substrate. A photopolymerizable composition layer is formed on the substrate by laminating the photopolymerizable composition while applying heat thereon.

As mentioned above, this photopolymerizable composition layer is extremely active against light rays in a wide range from ultraviolet light to visible light.
This is then pattern-exposed to various types of light such as ultra-high pressure, high pressure, and low pressure mercury lamps, metal halide lamps, xenon lamps, carbon dioxide lamps, sunlight, fluorescent lamps, and white electric lamps through a predetermined photomask. Furthermore, by pattern exposure to various types of ultraviolet and visible laser beams, even if the composition layer is as thick as 10 to 1001 inches, the sensitivity characteristics are as good as when the composition layer is as thin as several microns. It can be hardened to After this pattern exposure, the unexposed portions are removed with an alkaline aqueous solution and developed to obtain a desired cured pattern.

〔Effect of the invention〕

As described above, in this invention, by using a specific film-forming polymer substance and a specific photopolymerization initiator in combination, it is highly sensitive to ultraviolet light and visible light,
It is also possible to provide a highly sensitive photopolymerizable composition that is sensitive to laser beams. According to this composition, even when it is formed into a layer with a thickness of about 10 to 100/'1, there is no significant decrease in sensitivity characteristics, so it is used as a dry film photoresist for manufacturing printed circuit boards. It can also be used without any problems and is also suitable as a material for laser patterning of printed circuit boards, which has attracted particular attention in recent years. Moreover, according to this composition, development after pattern exposure can be carried out using an alkaline aqueous solution, so it is possible to save resources and improve hygiene in the development stage.

[Examples] Below, examples of the present invention will be described in more detail. In addition, in the following, parts shall mean parts by weight. Furthermore, Polymer A and Polymer B as film-forming polymeric substances used in the following Examples and Comparative Examples were synthesized by the following method.

<Polymer A> Styrene 5:l (0.5 mol), maleic anhydride 49y (0.5 mol) and methyl ethyl ketone 401' were charged in a reaction vessel No. 11, and after uniformly dissolving and mixing, azobis was added as a polymerization initiator. Isobutyronitrile 0.75! ? was added, and the mixture was stirred and reacted at 60°C for 3 hours while flowing nitrogen gas. After reflection, the mixture was cooled to room temperature and dropped into 6 times the amount of n-hexane with vigorous stirring to precipitate a polymer.

The polymer after filtration and drying is further mixed with methyl ethyl ketone.
- It was purified by two reprecipitations with hexane.

Polymer A thus obtained had a copolymerization ratio of styrene and maleic anhydride of 1:1.3, an average molecular weight of about 60,000, and a yield of about 9,096.

Polymer B> In a reaction vessel of 11, 30y of polymer A, 450y of dehydrated pyridine, 30y of 2-hydroxyethyl methacrylate
0y, imidazole 0.57 and hydroquinone 9y
was added and reacted at 65°C for 6 hours, then cooled to room temperature. This reaction solution was mixed with 6 times the volume of dilute acetic acid aqueous solution (5 to 8% by weight).
was added dropwise to precipitate the polymer, which was then filtered and dried. Thereafter, reprecipitation was repeated twice using methyl ethyl ketone and a dilute acetic acid aqueous solution to purify the polymer.

Elemental analysis revealed that the polymer B thus obtained had a 2-hydroxyethyl methacrylate introduction rate of approximately 6.
0%, i.e. about 60% of the acid anhydride groups in the polymer.
It was confirmed that the above methacrylate was bound to.

Example 1 8100 parts of polymer, 100 parts of pentaerythritol triacrylate, mixed organic dye represented by general formula (II), (IID (Y = S, R3 = C2H)
5, R4, Rs"H), 4 parts of N-phenylglycine, and 500 parts of methyl ethyl ketone were uniformly mixed and dissolved to prepare a solution of the highly sensitive photopolymerizable composition according to the present invention.

Example 2 An organic dye was mixed with a mixed organic dye represented by the general formula ([1), ([3] [Y=S, R3=7 cetyl group, R4, R5
=CI! ] A solution of a highly sensitive photopolymerizable composition having the same composition as in Example 1 was obtained except that the amount was changed to 4 parts.

Example 3 An organic dye was mixed with a mixed organic dye represented by the general formula (1, (ID) [Y=0, R3= (CH2)30CH3,
R4=CH3, R5=H] A solution of a highly sensitive photopolymerizable composition having the same composition as in Example 1 was obtained except that the composition was changed to 4 parts.

Example 4 Organic dye is an organic dye represented by general formula (1) and Y=
O1X = H, R, = C) T,, CH(OH) C
A solution of a highly sensitive photopolymerizable composition having the same composition as in Example 1 was obtained, except that the amount was changed to 4 parts.

Example 5 An organic dye was converted into an organic dye represented by the general formula (Il [Y=
O, X=Br, R4= (CH2)3N(C2H5
)2, R2=N(C2H5)2] A solution of a highly sensitive photopolymerizable composition having the same composition as in Example 1 was obtained except that the amount was changed to 4 parts.

Example 6 An organic dye represented by the general formula CI) [Y=
0,X=CI! ,R,=CH2CH(C2H5)C+H
*, R2=N(:C2H3)2] A solution of a highly sensitive photopolymerizable composition having the same composition as in Example 1 was obtained, except that the amount was changed to 4 parts.

Example 7 An organic dye represented by the general formula (1) (Y=
S, X=81 J=(CH2)30CH(CH+)
A solution of a highly sensitive photopolymerizable composition having the same composition as in Example 1 was obtained, except that the amount was changed to 4 parts.

Example 8 An organic dye represented by the general formula (I) 1Y=
S 1 X=Cff, R,=(CH,)20CH3
, R2= C) I, l,! ] A solution of a highly sensitive photopolymerizable composition having the same composition as in Example 1 was obtained, except that the composition was changed to .

Example 9 100 parts of trimethylolpropane triacrylate instead of 100 parts of pentaerythritol triacrylate
A solution of a high-sensitivity photopolymerizable composition having the same composition as in Example 1 was obtained, except that 50% of the photopolymerizable composition was used.

Example 10 Instead of 100 parts of pentaerythritol triacrylate, Aronix M-8 (trade name, manufactured by Toagosei Chemical Industry Co., Ltd.), which is commercially available as oligoester acrylate, was used.
A solution of a highly sensitive photopolymerizable composition having the same composition as in Example 1 was obtained except that 100 parts of 030 was used.

Comparative Example 1 A solution of a photopolymerizable composition having the same composition as in Example 1 was obtained, except that 100 parts of Polymer A was used instead of 100 parts of Polymer B.

Using each of the solutions according to Examples 1 to 10 and Comparative Example 1, a photopolymerizable composition layer with a thickness of 2μ or more was applied to the copper surface of a copper-clad laminate of a printed circuit board whose surface had been cleaned. A thick photopolymerizable composition layer was formed and subjected to the following sensitivity characteristic test.

The 2μ thin photopolymerizable composition layer was formed by applying each solution directly to the copper surface of the laminate and drying it in an SO'C for 1 minute. On the other hand, the formation of a thick photopolymerizable composition layer having a thickness of 2Q) ty+ or more requires a thickness of 25/''
Each solution was applied to a specified thickness on a transparent polyester film and dried at 80°C for 3 minutes to form a dry film photoresist.
This was done by laminating using a hot roll at 00°C.

<Sensitivity characteristic test>
．． Spot exposure was carried out using a 5W Ar ion laser light source with a wavelength of 488 nm with a beam diameter of 1.25++ m and varying the exposure amount. After this exposure, the unexposed portions were removed and developed using a triple dose % sodium metasilicate aqueous solution, and the exposure amount at which the diameter of the obtained spot coincided with the beam diameter (1.25 mm) was defined as the sensitivity.

The results were as shown in Table 1 below.

Table 1 As is clear from the above results, the sensitivity characteristics of the photopolymerizable composition of Comparative Example 1 decrease significantly as the thickness increases, whereas the photopolymerizable compositions of Examples 1 to 10 of the present invention It can be seen that the photoresist exhibits high sensitivity even when the thickness of the photoresist increases, and that it can be sufficiently applied as a dry film photoresist that requires a thick layer.

Example 11 Highly sensitive photopolymerizable product having the same composition as Example 1 except that 2 parts of 2,4,6-dolystrichloromethyl-1,3,5-triazine was used instead of 4 parts of N-phenylglycine. A solution of the composition was obtained.

Example 12 An organic dye represented by the general formula (I) [Y=
0. X=H, R1=C)12CH(OH)CH3, R
A solution of a highly sensitive photopolymerizable composition having the same composition as in Example 11 was obtained, except that the amount was changed to 4 parts [2=OCH3].

Example 13 An organic dye represented by general formula (I) [Y=
O,X=C1%R1=(CH2)20 parts%R2=N(C
A solution of a highly sensitive photopolymerizable composition having the same composition as in Example 11 was obtained, except that the amount was changed to 4 parts.

Example 14 An organic dye represented by the general formula CI+ [Y=
O1X=Ce, R,=CH2CH(C,,R5) C
4)1. , R2=N(C,,H,R) A solution of a highly sensitive photopolymerizable composition having the same composition as in Example 11 was obtained, except that the amount was changed to 4 parts.

Example 15 100 parts of trimethylolpropane triacrylate instead of 100 parts of pentaerythritol triacrylate
A solution of a high-sensitivity photopolymerizable composition having the same composition as in Example 11 was obtained, except that 50% of the photopolymerizable composition was used.

Example 16 Instead of 4 parts of N-phenylglycine, 2-methyl~4
- A solution of a highly sensitive photopolymerizable composition having the same composition as in Example 1 was obtained, except that 2 parts of 6-pisdolichloromethyl-1,3,5-triazine was used.

Example 17 High-sensitivity photopolymerization with the same composition as in Example 1, except that 2 parts of 2,4,6-dolystribromomethyl-1,3,5-triazine was used instead of 4 parts of N-phenylglycine. A solution of the sexual composition was obtained.

Example 18 Highly sensitive photopolymerizable product having the same composition as Example 1, except that 2 parts of 2,4,6-dolysdichloromethyl-1,3,5-triazine was used instead of 4 parts of N-phenylglycine. A solution of the composition was obtained.

Comparative Example 2 A solution of a photopolymerizable composition having the same composition as in Example 11 was obtained, except that 100 parts of Polymer A was used instead of 100 parts of Polymer B.

Using each of the solutions of Examples 11 to 18 and Comparative Example 2, a photopolymerizable composition layer of a predetermined thickness was formed in the same manner as described above, and a sensitivity characteristic test was conducted on this layer in the same manner as described above. The results were as shown in the accompanying @2 table.

7,・′ 7/″ /′ Table 2 As is clear from the above results, Example 11 using a 2,4,6-substituted-1,3,5-triazine compound as a combined component with an organic dye Also in the photopolymerizable compositions of ~18, Examples 1 to 1 using the N-phenylglycines
It can be seen that the same excellent sensitivity characteristics as in the case of 0 can be obtained.

Claims (1)

[Claims] (1) In a photopolymerizable composition containing a film-forming polymer substance, a monomer or oligomer having at least one addition-polymerizable carbon-carbon double bond in one molecule, and a photopolymerization initiator, the above polymer The substance is a copolymer of styrene and maleic anhydride with a hydroxyl group in the molecule (meth)
It consists of a polymer obtained by reacting an acrylic acid ester monomer, and the above photopolymerization initiator has the following formula (
I ), (II) (III); ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) ▲There are mathematical formulas, chemical formulas, tables, etc. Yes▼...(III) [In the formula, R_1 is an alkyl group or a substituted alkyl group, R
_2 is a hydrogen atom, methyl group, alkoxy group or amino group (including substituted amino groups), R_3 is an alkyl group, substituted alkyl group or acetyl group, R_4 is a hydrogen atom, halogen atom or methyl group, R_5 is a hydrogen atom, halogen atom, methyl group, alkoxy group or amino group (including substituted amino groups), X is a hydrogen atom or a halogen atom, Y
is an oxygen atom or a sulfur atom] and N-phenylglycines and/or 2,4,6-substituted-1
- A highly sensitive photopolymerizable composition comprising a 3,5-triazine compound.