JPS5810737A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive resin composition not restrained in photohardening reaction even when it is exposed to light in the air, by incorporating a vinyl copolymer of a specified (meth)acrylate and a radically polymerizable monomer, a multifunctional olygomer, and a photosensitizer. CONSTITUTION:A resin composition contains (A) a vinyl copolymer composed of 10-70wt% (meth)acrylate having a cyclic unsaturated group represented by formulaIin which R1 is H or CH3; R2 is formula II, III, or IV; R3 is H or CH3; m is 0-6; and when m=1, n=2-5, and when m=2-6, n=2: and 30-90wt% radically polymerizable monomer as constituent units, (B) a multifunctional olygomer containing a vinyl group in the terminal of the molecule, and (C) a photosensitizer. As the (meth)acrylate to be used having the cyclic unsaturated group, 8(9)-acryloxytricyclo[5.2.1.0<2.6>]-4-decene, etc. are embodied.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive resin composition which has the property of being cured by the action of photoresist. A substance that obtains a chemical-inconsistent dura t*lEL by exposure to light is generally called 7-otoresist, and is used in industrial applications such as the minute hand O of photolithography and the mark 11m.

In many of the various photosensitive resin compositions, the social photosensitive layer rLw5 is stretched in the presence of oxygen. It is troublesome to have to block out oxygen, and there is a desire for a sensory resin composition that can be irradiated with light in the atmosphere without being affected by oxygen.

The great invention builds on the above-mentioned prior art, and aims to provide a novel resin composition 1 that does not suppress photocuring [j6] even when exposed to light in the air. An integer that satisfies the W4 coefficient.

■When -1, mwm2~S%ta-When 2~6, -
10 to 70% by weight of an ester of acrylic acid or methacrylic acid @/WI having a cyclic unsaturated group represented by -2°) and a radically polymerizable monomer S-I.

% by weight as a constituent unit of vinyl copolymerized photosensitive resin footwear.

Acrylic acid or methacrylic acid with a cyclic unsaturated group used in the great invention! Among the 0 esters, if the cyclic unsaturated group is O, which satisfies the above general formula, 5(S)-acryloxytricyclo[s, z,
x, o”・6]-Mato-decene (This is 8-acryloxytricifacrylo-citricyclo[5,!, 1.0 snow-
]-4-Means both dasen・Hereinafter the same shall apply. ).

8(I)-Methacryloxytricyclo (S, Z, t01
°0]-4-decene (common name, dicyclopentenyl methacrylate), 811)-acryloxytricyclo(5
，! , 1.0"・6]-2-methyl-4-decene, 5(
S)-acryloxytricyclo(5,2,1,0'''
)-3-methyl-4-decene, all)-methacryloxytricyclo[! ! , 2.1. O! l@)-1-methyldacene, cyclo(9)-methacryloxytricyclo(i
,z,x.

6 m+@ ) -3B-methyl-4-decene and the like.

When m in the general formula is 1, 2-dicyclopentenoxyethyl acrylate (2-dicyclopentenoxyethyl methacrylate), 2-dicyclopentenoxyethyl methacrylate (2-dicyclopentenoxyethyl methacrylate), 2-dicyclopentenoxypyl methacrylate (the same applies hereinafter), 3
- dicyclopentenoxy isodatyl (meth)acrylate, 3-dicyclopentenoxyneopentyl (meth)acrylate, etc., and when the argument is IO, diethylene glycol - dicyclopentenyl ether acrylate tolu ether Methacrylate, triethylene glycol■
Seven-wheel cyclopentenyl ether f sy (meth)acrylate, tetraethylene glycol monodi cyclopentenyl ether (meth)acrylate, pentaethylene glycol Tomigami dicyclopentenyl (meth)
Examples include acrylate, hexaethylene glycol monomer dicyclobetanthene ether (meth)acrylate, and the like.

Furthermore, the cyclic unsaturated group possessed by the ester represented by the above general formula includes dicyclopentele, wamOt
), specific examples include 30-acryloxy-1-cyclopentene, 3(4)-methacryloxy-1-cyclopentene, 4(Il-acryloxy-1-cyclohexene%4(Iil-methacryloxy-1-cyclopentene)). Hexene, 5(1)-acryloxybicyclo[2,2,1]-2
-hebutene, 6 mourning) - methacryloxybicyclo (!,!
, 1)-2-heptene and the like.

However, these esthetics 7 & 10 have excellent defecating properties in the presence of air, which is thought to be based on the dimatoid bond having the above-mentioned cyclic non-maltable group O, and excellent defecating properties of hardened doxane. 8(-1-acryloxy) 95y9tl (S
, 2 , 1 , 0''']-4-9'sen, ・(It-
Methacryloxytricyclo (S, Z, t, *, a)
-, -decene and 2-dicyclopentenokylethyl (meth)acrylate are particularly preferably used.

Peng who fulfills the above general formula is 1 to 6 esthetics A / Keichikin,
Tricyclo(1,2,1,0″, @'3 3-decenol (common name, dicyclopentenyl, 1.ol・0
] Methysy-3-decen-ol, methyl-cyclopenten-1-ol, cyclohecan-1-ol,
2-Methylcyclohexen-1-ol, bicyclo(!, 2.
1) -3-/thiru-2-hebutene-oh #rumor O The product obtained by reacting ethylene oxide, propylene oxide, etc. with ethylene oxide, %j! #)IlI is produced by a method of reacting K(meth)acrylic acid to esterify it.

The vinyl copolymer used in the present invention contains 10 to 70% by weight of the ester represented by the above general formula (hereinafter, % is coulometric %).
shall be shown. ). If it is less than 10%, the resulting photosensitive resin composition will be affected by the exposed 0III and airborne 0I11 elements, and the one-light reflection 6 will be easily suppressed, and if it exceeds 70%, the copolymer will tend to gel at the time of coalescence. The compatibility between the vinyl copolymer and other mixture components is poor.

The radically polymerizable monomer to be copolymerized with the ester represented by the above general formula includes methyl (meth)acrylate, ethyl A/(meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. (Meda) 199th-alkyl ester, styrene α
- Alkenylbenzenes such as methylstyrene and vinyltoluene, 2-hytomythyl (7) acrylate, glycidyl (meth)acrylate, and K is vinyl acetate, acridinitrile, methacryloethryl, acrylic acid, methacrylic acid, Conventionally known 4Os such as itaconic acid, maleic anhydride, acrylamide, methacrylamide, methacryl A/@-dime7A/aminoethyl, and styrene sulfonic acid are used.

These radically polymerizable monomers are used as structural units in the vinyl copolymer in an amount of 30 to 90%.

The above-mentioned vinyl copolymer can be obtained by the conventionally known violet method, solution polymerization, suspension polymerization, or emulsion type hK, but the solution polymerization method is usually preferably used. Examples include pro, It)-l, methyl cellosolve, methyl cellosolve, butyl cellosolve acetate, ethyl carpitol, acetone, methyl cotyl ketone, and ethyl acetate A/41, and these may be used alone or in appropriate mixtures. The molecular weight of the vinyl copolymer is determined appropriately depending on the use of the monomer composite material, but generally ranges from K100 to 10.
It is preferable that the vinyl copolymer is in the range of Fiso 00 to 90% in the total composition.

Examples of the polyfunctional oligomer containing a vinyl group at the molecular terminal in the invention include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and molecular weight 200 to 5.
00 polyethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate with a molecular weight of 200 to 500, glycerin tritacrylate, trimethylol pro/acrylic triacrylate, pentaerythritol triacrylate,
In addition to methylene bis-acrylamide, ethylene bis-acrylamide, 1,6-hexane bis-acrylamide, ethylene bis-methacrylamide, ethylene dalycol bis-diacryl carbonate, diacryl phthalate, etc.
Cretane polymer having an incyanate group at the end of the molecule and a compound containing a vinyl group and active hydrogen in one molecule; Compounds containing a large amount of functional groups such as 411011 in conventional photosensitive resin compositions, such as reactants with 9-fluoric acid, are preferably used in an amount of 0%. The reason for this is that if the amount of polyfunctional oligomer is less than 10%, the photocuring speed will be slow. This is because there is a tendency for the value to increase.

11 Kutou Sensitizer Co., Ltd., Mo-Ming composition This plays the role of causing a photopolymerization reaction in the spring ink by photoexcitation when the Ktli light is irradiated with it. Various O%O is used. Typical examples include benzoin, α-methylbenzoin, a-allylbenzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin monomethyl ether, acetophenone, benzophenone, P-frombenzophenone, diphenyl disulfide, Mention may be made of benzyl, diacetyl and Kurani A/4I nitrate. One or more of these 0 photosensitizers can be used in one Oi unit. Such a photosensitizer may be used in an amount of ao01 to 10g6 in the total amount of the photosensitive resin composition. If the amount added is less than 0.01%, it is disadvantageous in practice because the photo-severity becomes extremely slow; on the other hand, if it exceeds 10%, no particularly significant sensitizing effect can be expected. It becomes uneconomical.

In order to improve the storage stability of the composition of the present invention, usually
It is preferable that a polymerization inhibitor is contained in an amount of 4001 to 2% of the total composition, and examples of the inhibitor include benzoquinone, 2,5-ditheludebenzoquinone, hydroquinone, and hydroquinone. Conventionally known compounds such as trimethyl ether, catechol, β-su7tol, monotart-butyβ-hydroquinone, and pyrogallol can be mentioned.

Furthermore, the composition of the present invention may contain rheological property modifiers such as silica fine powder, pigments, dyes, fillers, plasticizers, etc., as well as necessary KI6, and lII used is usually obtained by solution polymerization. The above polyfunctional oligomer, photosensitizer, polymerization inhibitor, plasticizer, etc. are added to the obtained copolymer solution having a cyclic immobilized group, and the obtained solution of the photosensitive resin composition is used as a base material. Dry the coating cost. When the film after exposure is immersed in an aqueous developer, a base such as alcohol amine is added to the solution of the composition in advance to increase the dispersibility and solubility of the composition in the developer. You can leave it as is.

Exposure is generally carried out by activator IIIK with a wavelength of 1800-7000λ, and the light #l sensitizer 011
1 [K] Although different types of lamps must be used, usually solar rays, tungsten lamps, vertical arc lamps, mercury lamps, ultraviolet fluorescent lamps, etc. are used.

The present invention I1-Party Resin Composition Co., Ltd. has the above-mentioned structure, a vinyl copolymer containing an ester having a specific & cyclic unsaturated group, a polyfunctional oligomer containing a vinyl group at the molecular end, and photosensitization. Since it contains a chemical agent, a cross-linking reaction occurs even in the presence of oxygen, and a cured product with excellent chemical resistance is obtained.

Thus, the photosensitive resin composition of the present invention can be used for forming photographic images, making printing plates, making plates, making printed circuits, printing materials, paper, wood, etc.
It is advantageously used in human milk applications such as gold@0 coating.

Next, the present invention will be explained in detail with reference to Examples, but the invention is not limited thereto.

Reference Example 1 A 91-ton cellar equipped with a stirrer, a fishometer, a dropping funnel, a cooling pipe, and a nitrogen pipe.
8 (also Fi9)-acryloxytricyclo[5, Goose, 1.0'', @) in which azobisisobutyronitri #8f was dissolved at 188°C in a nitrogen stream.
4-decene 72t, methacrylic 931f, butyl methacrylate 50t, 2-ethylhexyl acrylate 47
and lacrylic mercabutane were added dropwise over a period of 3 hours, and stirring was continued for 2 hours to obtain a solution for the copolymerization reaction.

Reference Example: ~4 The type and amount of each monomer in Reference Example IK are as shown in Table IK. .

* I +18 (or 9)-acryloxytricyclo(5,2,
,1,0'・6]-4-decene.

Example! Add 100 fK pentaerythritol triacrylate) 35F of the copolymer solution obtained in Reference Example 1, benzoin isopropyl ether Sf, hydroquinone methyl ether aiF, and 10 dimethylaminoethanol to the same 1t Cerapul 7 rasp as in Reference Example 1, and mix uniformly. A photosensitive resin solution was obtained.

The composition was dried on a polished A8 inch zinc plate.
Coat with a wire coater so that the film thickness is 2pK,
A zinc plate coated with the photosensitive composition was obtained by drying at 0°C for 10 minutes.

Lightly place a negative film on the surface of the photosensitive zinc plate.
After exposing for 1 minute from a distance of 53 mm using a chemical lamp of OW, I immersed it in a 30% aqueous solution of gucci cellosolve and developed it. Insoluble and clear positive images were obtained.

Next, the zinc plate was etched with a commercially available etchant that had been dried at 120°C for 5 minutes, and a white zinc plate with only the convex parts stably coated with the photosensitive resin was obtained, which was the same as in Example 1. IL cell/(Reference example 2 in a rubble flask)
Copolymer solution obtained in 100fK pentaerythritol triacrylate 35f, benzoin isopropyl ether 5f1)/hydroquinone monomethyl ether alt,
Add 10 f of dimethylaminoethanol and dissolve uniformly.
A photosensitive resin solution was obtained. The composition was applied to a printed wiring board covered with copper foil in the same manner as in Example 1, dried, and then a negative film was lightly placed on it, followed by exposure and development. A clear positive image was obtained. . The board vt12
After drying at 0° C. for 5 minutes, the copper foil was etched with a ferric solution and the resist film was peeled off with methylene chloride containing 30 g of methanol to obtain a good printed wiring board.

Example 3 Into a 1t Serapur 72 tube similar to Example 1, 100 fK of the copolymer solution obtained in Reference Example 3 was added.
, dimethylaminoethanol tore was added and dissolved uniformly for 1 s to obtain photosensitivity -***.

The composition was irradiated in the same manner as in Example 2, and the portion became insoluble in the solvent.Furthermore, when a printed wiring board was irradiated in the same manner as in Example 2, the original pattern showed 41L #IIIW! 4 printed wiring boards were obtained.

Comparative Example 1 Reference side 4 was attached to 1t separable 7 lasco similar to Example 1.
To 100 f of the copolymer solution obtained in step 1, 35 t of pentaerythritol triacrylate, 5 t of benzoin isopropyl ether, 10 t of hydroquinone methyl ether + Qlf, and 10 t of dimethylamino ethanol were added and uniformly dissolved to obtain a photosensitive resin solution.

A zinc white board was remade using the composition in the same manner as in Example 1. However, when the exposed composition was developed by immersing it in a developing wave, the image had a wind cylinder effect without the influence of residual air.

I made a printed wiring board at the same @ as Yuki.

When one composition after exposure was immersed in a developer and developed,
Perhaps due to the influence of residual air, a clear positive image could not be obtained due to insufficient supervision of the photocuring force, and a 1 ml difference in the image was observed. The remaining image was also considerably removed from the WIAK steel foil etched with a ferric chloride solution, and a printed wiring board with good handling could not be obtained.

patent applicant Sekisui Chemical Co., Ltd. Representative 5F13 Motori

Claims (1)

[Claims] In @()111, m is an integer that satisfies the following equation. m-1/)! 14m-! ~s1m-ax ~so time #fm1m! , ) having a cyclic unsaturated group represented by A/al! A vinyl copolymer having as constituent units 10 to 70% by weight of an ester of 112. The sensory resin composition according to item 111, which contains 0% by weight. Turtle Polyfunctional oligomer content in the total composition is 10-7
0% by weight of the photosensitive resin composition according to item 1 or item 2.