JPS5854337A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive resin composition unrestrainable in photohardening reaction even when exposed in the air, by using a mixture of a specified polymer having ethylenically unsatd. bonds in the side chains, a photosensitizer, and when needed, a functional olygomer having a vinyl group in the end of the molecule. CONSTITUTION:A photosensitive resin composition contains (A) a polymer having ethylenically unsatd. bonds in the side chains, (B) a photo sensitizer such as benzoin, and when needed, (C) a multifunctional olygomer having a vinyl group in the end of the molecule, such as diethylene glycol diacrylate. The polymer (A) is obtained by adding an ethylenically unsatd. compd. contg. an oxilane ring to the carboxyl groups of a copolymer having as structural units unsatd. carboxylic acid and (meth)acrylate contg. a cyclic compd. of formulaIin which R1 is H or methyl; R2 is one of formula II-V; R3 is H or methyl; m is an integer of 0-6; when m is 1, n is 2-5, and when m is 2-6, n is 2.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive resin composition that has the property of being cured by the action of light. A substance that can form a hard film that is insoluble in chemicals when exposed to light is generally called a photoresist, and is used in industrial fields such as printed circuits as well as photolithography.

The photosensitive reaction of many of the various photosensitive resin compositions is suppressed in the presence of oxygen. Since it is troublesome to have to provide a layer, there has been a desire for a photosensitive resin composition that is less affected by oxygen and can be irradiated with light in the atmosphere.

In view of the above-mentioned prior art, the present invention aims to provide a novel resin composition in which the photocuring reaction is not suppressed even when exposed to light in the air. Contains a polymer for binding t*r, a photosensitizer, and optionally a functional oligomer containing a vinyl group at the end of 19 molecules! The polymer having an ethylenically unsaturated bond in the side chain is an integer of 10 6 , and n is an integer that satisfies the following relationship.

When am = 1, l'l m = 2-6, m
= 11mx when 2~flh! ,) A copolymer containing an ester of acrylic acid or methacrylic acid having a cyclic unsaturated group, an unsaturated carboxylic acid, and a tsi* unit, in which an oxyphrine ring-containing ethylenically unsaturated compound is added to the carboxyl group. A photosensitive resin composition is characterized in that:

Among the esters of acrylic acid or methacrylic acid having a cyclic unsaturated group used in the present invention, when the cyclic unsaturated group is dicyclobentenyelium w4 and m in the above general formula is O, 8191-1 chlorochlorotricyclo(5,2 ,1,
0m-@)-4-decene (this is 8-1 acryloxytricyclo(5,2,1,Oh・]-)4-dace and 9-acryloxytricyclo(5,2,16gs,@) --4-
Desen means both. Same hereafter), 8(-)-methacryloxytricyclo(1,!, IQl, .]-]4
−Decene general name, dicyclopentenylmethacryl)
)% 8 (91-acrylokiretricyclo(5,!, 1.
O snow-6]-2-methyl-4-decene, 8(91-acryloxytricyclo(s, z, i, om-・]-]-]3-
Methyl-4-dacene 81@)-methacryloxytricyclo[5,2,1,611)-z-methyl-decene, II
till-Methacryloxytricif El (5,2ml
．． 0s*.]-]3-methyl-4-decene.

Father, when m in the above general formula is 10, 2-dicyclopentenoxyethyl acrylate (clopentenoxyethyl methacrylate, 2-dicyclopentenoxyprobi A/(meth)acrylate (this is 2-dicyclopentenoxyethyl methacrylate) Means pentenoxypropyl acrylate and 2-dicyclopentenoxypropyl methacrylate. The same applies hereinafter.)
, 3-dicyclopentenoxyisobutyl (meth)acrylate, 3-dicyclopentenoxyneobenchi A/(meth)acrylate, etc., and when m is tI, diethylene glycol = 7 no = dicyclopentenyl ether acrylate ethylene glycol = mono = dicyclobentenyl ether (methacrylate),) 11 ethylene glycol = mono =
Dicyclopentenyl ether (meth)acrylate, tetraethylene glycol 7-dicyclopentenyl ether & (meth)acrylate, pentaethylene glycol mono-dicyclopentenyl, (meth)1 acrylate, hexideethylene glycol seno- Examples include dicyclopentenyl ether (meth)acrylate.

Furthermore, the cyclic unsaturated group represented by a in the ester represented by the above general formula is dicyclopentenyl, and a specific example when m=0 is H13141-7cryloxy1-cyclopentene%3(41-methacryloxy-1- cyclopentene, 4(61-acryloxy-1-cyclohexene, 4+il-methacryloxy-1-cyclohexene,
5i61-1 Chryloxypicyclo(2,2,1)-2-
hebutene, 5(@l-methacryloxybicyclo[2,2
, 1)-2-hegetene and the like.

Among these esters, 8 (91-acrylic lokiretricyclo(5,2,1,0
"I・]-]4-daceneS (S)-methacryloxytricyclo(5,2,1,0s...]-]4-decene2-
Dicyclopentenoxyethyl (meth)acrylate is particularly preferably used.

In general, the ester in which m is 1 to 6 in the above general formula is
Q/ri-Kl(5,2,1,Ol-3-decenol(
Common name, dicyclopentenyl, 2.1.0) Methyl-3-decen-ol'2-methyl-cyclopenten-
1-ol, cyclohexene-1-o, 12-methylcyclohecan-l-ol, bicyclo(2,2,1)
-2-hebutenol, bicyclo(2,2,1)-3-
It is produced by a method in which a good product obtained by reacting an alcohol such as methyl-2-heptenol with ethylene oxide, propylene oxide, etc. is further reacted with (meth)acrylic acid to esterify it.

A copolymer of an ester represented by the above general formula, an unsaturated carboxylic acid, and a t** unit (
It is preferable that the ester (hereinafter referred to as a pace polymer) is contained in a range of 3 to 50% by weight (hereinafter, % indicates 1% by weight) of the ester represented by the above general formula. 396
If the amount is less, the resulting photosensitive resin composition will be affected by oxygen in the air during exposure, and the photosensitive reaction will be more likely to be suppressed.
If it exceeds 0%, it is easy to gel during the synthesis of a polymer having ethylenically unsaturated bonds in the side chain (also, when the polymer having the ethylenically unsaturated bonds and other exposure ingredients added as necessary) There is a tendency for customer friendliness to deteriorate.

In addition, the unsaturated carboxylic acids to be copolymerized with the ester represented by the above general formula include anhydrides and monoalkyl esters of polycarboxylic acids, and specific examples thereof include (meth)acrylic acid, itaconic acid, and polycarboxylic acid. monomethyl ester, monoethyl ester, monopropyl ester, motubutyl ester, etc. of maleic acid, maleic acid, fumaric acid, vinyl acetic acid, itaconic anhydride, maleic anhydride, maleic acid or fumaric acid, and these companies alone or They are used by appropriately mixing them. If the amount of unsaturated carboxylic acid in the pace polymer is too large, the polarity of the polymer will become extremely high and the glass transition temperature will rise, while the film formed from the photosensitive resin composition will become brittle. It is preferable that the unsaturated carboxylic acid t* component unit of the pace polymer H is contained in the range of 5 to 5096, since it does not exhibit the ability to merge.

In addition, other radically polymerizable monomers may be copolymerized with the pace polymer to adjust flexibility, and specific examples thereof include methyl acrylate, ethyl acrylate, and n-propyl acrylate. , inglovir acrylate, n-butyl acrylate, tert-butyl acrylate, n-hexyl acrylate, garoctyl acrylate, acrylic w1
Acrylic acid alkyl esters such as (2-ethylhexyl), methyl methacrylate, ethyl methacrylate, methacrylate-provil.

Isopropyl methacrylate, goutyl methacrylate,
Tertiary glutyl methacrylate, utohexyl methacrylate,
Examples include methacrylic acid alkyl esters such as n-octyl methacrylate and methacrylic acid (2-ethylhexyA/), styrene, α-methylstyrene, alkenylbenzenes such as vinyltoluene, vinyl acetate, acrylonitrile, and methaqlonitrile.

The above base polymer can be obtained by a conventionally known polymerization method, but a solution polymerization method is usually suitably used. Specific examples of organic solvents used at that time include pro/4-nol, methyl cellosolve, butyl cellosolve, buty cellosolve. Heptatate, ethyl calpitol, acetone, methylethylgtone, ethyl acetate, etc. are available, and these can be used alone or in appropriate mixtures.

In the present invention, preferable examples of the oxirane ring-containing ethylenically unsaturated compound added to the carboxyl group in the base polymer include Aku1371/acid glycidyl,
Examples include glycidyl methacrylate, acrylic glycidyl ether, and monoalkyl ester of monoglycidyl maleate.

The addition reaction of the oxykune ring-containing compound to the carboxyl group in the base polymer is usually carried out in a solution, and ketones, esters, alcohols, ether A/s, etc. are used as the solvent, and are particularly suitable. Examples include alcohols having 3 to S carbon atoms and mixed solvents containing the alcohol-A/ as a main component and the above-mentioned solvents. Moreover, trimethylpendylammonicum hydroxide or the like is preferably used as a reaction catalyst.

In addition, in carrying out this reaction, in order to suppress vinyl type addition polymerization of the oxirane ring-containing ethylenically unsaturated compound,
Preferably, a polymerization inhibitor such as hydroquinone is present in the reaction system.

The oxirane ring-containing ethylenically unsaturated compound has an ethylenically unsaturated bond tW in the side chain generated by the above reaction.
From the viewpoints of the photosensitive speed of the polymer, adhesion to the substrate, so-called alkali developability that can be easily dissolved in an alkaline aqueous solution, and the toughness peak of the film, it is preferable that the amount of a03 to LO equivalent to the carboxyl group in the base polymer is , particularly preferably Fi
ax~(L8 equivalent is added.

The molecular weight of the thus obtained polymer having an ethylenically unsaturated bond tW in the side chain is appropriately determined depending on the use of the photosensitive composition, but is usually in the range of r, ooo to SO, 000, preferably 1,000 to 10. The range is 000 to 000.

In addition, the photosensitizer plays the role of easily causing a photopolymerization reaction by photoexcitation when the composition of the present invention is irradiated with actinic rays, and various types can be used.
Typical examples include 2-ethylanttotsuquinone,
Benzoin, α-methylbenzoin, α-allylbenzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin-rich methyl ether, acetophenone, benzophenone, ? -Pro^benzophenone, diphenyl disulfide, benzyl, diacetyl,
Examples include cutunyl nitrate. These photosensitizers can be used in mixed VCs of lIl or Fi2 or more. Such a photosensitizer may be used in an amount of aoox-io% in the total amount of the photosensitive resin composition. Addition amount is a00
When it is less than 1%, it is practically disadvantageous because photopolymerization becomes extremely slow, and when it exceeds 1G96,
A particularly remarkable sensitizing effect cannot be expected, and it is uneconomical.

Examples of the polyfunctional oligomer containing a vinyl group at the molecular end, which can be used as necessary to increase the photocuring speed of the composition of the present invention, include diethylene glycol diacrylate,
Triethylene glycol diacrylate, tetraethylene glycol diacrylate, diacrylate of polyethylene glycol with a molecular weight zoo-soo, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, dimethacrylate of polyethylene glycol with a molecular weight of 200 to 500, glycerin trimethacrylate, Trimethylolpro, 4-triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, methylene bi-X 7 l
e) ~amide, ethylenebisacrylamide, 1ite6
In addition to -hequinane bisacrylamide, methylene bis-methacrylamide, ethylene glycol bis-diacryl carbonate, diacryl heptatalate, etc., cretan prepolymer having an isocyanate group at the end of the molecule and a vinyl group and a vinyl group in one molecule. Examples include reaction products with compounds containing active hydrogen, and reaction products of so-called epoxy resins having an engineered mexyl group at the end of the molecule with acrylic acid or methacrylic acid, and in particular, reaction products with compounds containing active hydrogen such as pentaerythritol tetraacrylate. Compounds with a large number of graves are preferably used. These may be used alone or in appropriate combinations, preferably 1% in the total composition.
Used in the range of 096 or less. The reason for this is that if the amount of polyfunctional 11th sesame exceeds 704, the toughness of the resulting photocured film tends to decrease and the influence of oxygen in the air tends to increase. The product preferably contains a polymerization inhibitor to improve storage stability, and examples of the inhibitor include:
Benzoquinone, 2. Examples include s-diphenyl-P-benzoquinone, hydroquinone, high Foquinone monomethyl ether, catechol, β-su7tol, mono-tert-butylhydroquinone, and pyrogallo-#◆ conventionally known ones.

The composition of the present invention may contain rheological property modifiers such as fine silica powder, pigments, dyes, fillers, plasticizers, etc., as necessary, and when used, the compositions mentioned above are usually added. A photosensitizer, and if necessary, a polyfunctional oligomer, a polymerization inhibitor, a plasticizer, etc. are added to a solution of a polymer having an ethylenically unsaturated bond in the side chain, resulting in a photosensitive resin composition. The acid solution is used as a base material, and the resulting photosensitive resin layer is dried using an active light source with a wavelength of 1800 to 70 GOA, and the light source is a photosensitizer. Depending on the type of agent, it is usually used in sunlight, tungsten lamps, carbon arc lamps, mercury lamps, etc. Since it contains a polymer in which an oxirane ring-containing ethylenically unsaturated compound is added to the base and a photosensitizer, the photosensitization reaction is not significantly suppressed even in the presence of oxygen, and therefore When irradiated with actinic rays, a crosslinking reaction occurs photochemically, resulting in a cured product with excellent chemical resistance such as organic solvent resistance, acid resistance, and Burka 11 resistance.

Thus, the photosensitive resin composition of the present invention can be used in a wide range of applications, including forming photographic images, making printing plates, making name plates, making printed circuits, and coating plastics, paper, wood, and metals. It is advantageously used in

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

Reference Example 1 200 ft of isopropyl alcohol was charged into a No. 11 Seragle flask equipped with a stirrer, a thermometer, a dropping funnel, a cooling tube and a nitrogen inlet tube, and a 10 ft melting spout of azobisisobutyronitrile was charged at 80°C in a nitrogen stream. 8 (or 9) -
Acryloxytricyclo (5, 2, 1, 0...) -]
4-decene 20f, acrylic acid 70f methyl methacrylate 30f, styrene &Of.

butyl acrylate) 20 y, acryloeth 1 Jpv
10 ft was added dropwise over 2 hours, reacted at 80°C for 5 hours, and then reacted at 85°C for 2 hours to obtain an inpropyl alcohol solution of a vinyl copolymer.

Next, add f f JL/ -t' to this vinyl octapolymer solution.
0 id (40% solution in methanol) itspt added,
After heating to 80°C, noide υquinone was added dropwise to 60 ft of glycidyl methacrylate dissolved in Q6F over 1 hour, and reacted at 80°C for 6 hours to form a polymer solution having %-ethylenically unsaturated bonds. Obtained.

The weight average molecular weight was 45,000.

Example 1 Polymerization temperature obtained in Reference Example 1 @205! and pentaerythritol tetraacrylate 2F.

2-ethyl anthraquinone (LaF3), 1-hydroquinone α02f, methyl violet (LO5) and methyl ethyl ketone xsyt were mixed and dissolved uniformly to form a photosensitive resin layer #L. This photosensitive solution was made into a polyester film with a thickness of 25 degrees. After coating, drying to obtain a polyester film with a photosensitive resin layer thickness of 25 μm.Next, polishing treatment and further attenuating treatment with dilute hydrochloric acid (1 g)
A polyester film having the photosensitive layer formed thereon was laminated on the layered printed marking box plate with a photosensitive resin layer interposed therebetween.

Place a negative film of 5yAt on the polyester film of this printed wiring board, and use zoow's chemical pump to attach 5a
After exposing for 1 minute from a distance of
Developed for 1 minute at 5°C. When I checked it with a photosensitive sensitivity t-step guide, I found that it had cured up to 8 stages but only 9, and a very clear positive printed wiring diagram was obtained.

Next, after drying the board at 120°C for 5 minutes, the copper foil of the board was corroded with a ferric chloride solution, and the resist was peeled off using methylene chloride containing 20% methanol - an extremely clear printed wiring diagram. was gotten.

Comparative Example 1 8(also #-j9)-acryloxy-tricyclo(5,2
,1,Ol·]-]4-de't> Instead of K-methyl memetallyl F, an inpropyl alcohol solution of a vinyl copolymer was obtained in the same manner as in Reference Example 1 except for the above. In place of the vinyl copolymer solution used in Reference Example 1, the above vinyl copolymer solution t- was used to obtain a polymer solution containing ethylenically unsaturated bond tubes in the side chain in the same manner as in Reference Example 1.

Weight average molecular weight i;j 4400G and 69.

A photosensitive resin solution was obtained in the same manner as in Example 1 using the above polymer solution instead of the polymer solution used in the example.

Using this photosensitive resin solution, a photosensitive resin layer was then applied to the copper foil on the printed wiring board in the same manner as in Example 1. In some cases, a copper printed wiring diagram was obtained.

Perhaps due to the influence of residual air, the curing step using the step guide, which is a measure of photosensitivity, has four steps, and some of the fine parts of the positive printed wiring image have fallen off, and the copper foil has been etched and the resist film has peeled off. The resulting copper printed wiring diagram was incomplete, with some of the thin parts falling off.

Claims (1)

[Scope of Claims] L#j1mlK A polymer having an ethylenically unsaturated bond, a photosensitizer, and optionally a polyfunctional oligomer containing a vinyl group at the end of the molecule is contained in the moss. A polymer with ethylenically unsaturated bonds t-W has the general formula CH1=CCO+CnHmaOh "T. When Peng=1, 1=2~S%vh=2~・Notoken is Saku=
3. ) An ethylenically unsaturated compound containing an oxirane ring in the carboxyl group in a copolymer containing an ester of acrylic acid or methacrylic acid having a cyclic unsaturated group shown in A photosensitive resin composition characterized by having ξ added thereto. The composition according to item 1. The composition according to item 1 or 2, wherein the turtle copolymer contains 5-SO weight % of unsaturated carboxylic acid as a constituent unit. ζ The polyfunctional oligomer content in the total l1vL product is 70
A composition of any one of the first to third terms 11 [Kε] which is at most % by weight.翫 Acrylic acid ester A/ is 8-1 chloromethane (5,2,1,9m,5)-4-dacene or Fi9-
Acryloxytricyclo(5,2,1゜03-1) -
The composition according to any one of Items 1 to 4, which is 4-f'sen.