JPS614039A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To reduce an exposure amt. necessary for insolubilizing a resin in developing water, and to obtain a sharp image by incorporating a PVAL type polymer having an alkyl or an F-contg. group on the terminal and a photosensitive agent. CONSTITUTION:The intended photosensitive material contains a PVAL type polymer having on the terminal an alkyl group, preferably, such as 2-24C alkyl, far preferably, 4-20C alkyl, and an F-contg. group. The F-contg. group used here is represented by the formula Rf-(X)m-, where m is 0 or 1, and Rf is selected from fluoroalkyl and fluoroalkyl ether, and X is selected from alkylene, alkylene ether, alkyleneamide, alkylene thioether, alkyleneimide, and alkyl ester. The use of such photosensitive resin compsn. can reduce an exposure amt. necessary for insolubilizing the resin in developing water, and it can form a sharp image. Peelability of a negative film, etc., from the surface of the obtained photosensitive resin can be improved, too.

Description

DETAILED DESCRIPTION OF THE INVENTION A1 Technical Field of the Invention The present invention relates to a photosensitive resin composition used in photolithography, processing of electronic parts, and the like. More specifically, the present invention relates to a photosensitive resin composition characterized by containing a polyvinyl alcohol polymer having an alkyl group or a fluorine-containing group at the end and a photosensitizer.

Bof used for photolithography and electronic parts processing, etc.
IJ+? =JLi7JLzD-JLz, ii-Kaoiya6-□5Yofat compositions include systems in which polyvinyl alcohol polymer is mixed with dichromate as a photosensitizer;
Instead of dichromate, which is a hazardous substance, a system in which organic photosensitizers such as diazonium salts and water-soluble azides are mixed, and an unsaturated compound with a photopolymerizable ethylenic double bond is added together with a photopolymerization initiator. Mixed systems are well known.

These photosensitive resin compositions are formed into a photosensitive film and then irradiated with light through a negative film to make the exposed areas insoluble in water, and then developed with water to dissolve and remove the unexposed areas to create the desired image. get.

Therefore, the photosensitive resin composition must have high photosensitivity,
It is required that the developability is good, that the insolubilized film in the exposed area has good adhesion to the base material, and that it does not peel off during development.

However, since the conventionally used polyvinyl alcohol polymers have low photosensitivity, it is necessary to use a large amount of a photosensitizer, especially an organic photosensitizer. However, organic photosensitizers are expensive, and it is desirable to use a small amount of them. Furthermore, when trying to obtain the desired image through long-term exposure, work efficiency decreases, and other problems arise, such as difficulty in obtaining a clear image. The f,t photosensitive resin composition is not satisfactory.

As a result of intensive studies in view of the above situation, the present invention has developed a photosensitive resin composition characterized by containing a polyvinyl alcohol polymer having an alkyl group or a fluorine-containing group at the end and a photosensitizer. We have found that this is true and have completed the present invention. That is, by using the photosensitive resin composition containing a polyvinyl alcohol polymer having an alkyl group or a fluorine-containing group at the end of the present invention and a photosensitizer, the amount of exposure necessary to make it insolubilized in developing water by light irradiation. can be reduced compared to conventional photosensitive resin compositions using polyvinyl alcohol polymers, and extremely clear images can be obtained.

Furthermore, one of the characteristics is that the surface of the photosensitive resin plate obtained using the photosensitive resin composition of the present invention has excellent peelability from films such as negative films.

First, regarding the photosensitive resin composition of the present invention, which contains a polyvinyl alcohol polymer having a terminal 1ζ alkyl group or a fluorine-containing group (hereinafter abbreviated as PVA polymer) and a photosensitizer. 1. Regarding the alkyl group in the PVA-based polymer having an alkyl group or a fluorine-containing group at the terminal, it is preferable that the number of carbon atoms is 24 or less based on fresh shellfish.

Specifically, $C2flP, c, B7, c4n steam c6n, F.

0ar(+F, O+.B21.0,2■25,(3,
4H2,,O+6Hs5,O,,H,,,Q2(In2
=, C24H49, etc. Among the above, when the number of carbon atoms is 4 or more and 20 or less, the resulting photosensitive resin composition has particularly excellent photosensitivity.

Furthermore, the fluorine-containing group in the PVA polymer in the present invention is represented by the general formula Bi[x)m (m-0 or 1), where E is represented by the following formula 0. It represents a fluorinated alkyl group or a fluorinated alkyl ether group represented by the following formula 0 or formula 2.

A(-0F2+...■(However, q==2~20, A
= If or q (however, t = 1 to 10) Specifically, 1l(CF2-+2, H(OF, +-4, H
(-OF2→2, ■+OF2+a, F, (70F2,
F (-OF2, F±CF2→, F+CF2-)-
5, F(-C1lI'2su6, F+0F2-h% F(
-OF2+8,ru.

In addition, X is an alkylene group represented by the following formula 0, 4,
,,Iyowa□,6A7. Ya22. -Care... Indicates any one of the alkylene amide group represented by A, the alkylene thioether group represented by Formula 2, the alkylene amide group represented by Formula 0, and the alkylene ester group represented by Formula 0 or [Phase].

+tat2 circles ・・・・・・■ (However, n = 1 to 5)
(70H2 major O child OB2 large...■(However, p=-
1-5, n = 1-5)-OON[(Elf2)m-
・-・-■ (However, n-1 to 5)" (8), -(OH2
) B +Qf12 *-n ・・・・・・■ [However, p-1 to 5, n-1 to 5, B-sulfur atom or oxygen atom (
However, when B is a sulfur atom, r = O or 1, and when B is an acidic compound, r = 1)) B.

(-ell, previous N Wataru (3112 large ......■ (However, p-1 to 5, n-1 to 5, B, = (3, to 05 alkylthio + an, -+, coo + aa2 nine・・・・・・
■(4m ship = 1~5, .=1~5)-000(
−0■2−q −−−−(J (however, n = 1 to 5
) Specifically, 0H2(J+OH2+-3, (CF12
-)-,,,-+OH2+4,+OL'+2N+CL
s4, -8+cH2chi2, (-cfi,, →i 8 (
aa2-3-,, product 3-8 +c11.2-), 0(-OH2s2,-8-
fCH, ±8-(-(3H2-)-2, -0ONIi-
(-CH2±, , +OH2+2COO(-CH2 3
, -coo+cn2su, etc.

The PVA-based polymer having an alkyl group or a fluorine-containing group at the end used in the present invention can be prepared by several methods, and may be prepared by using alkylthiols corresponding to the above-mentioned alkyl group or the above-mentioned general formula Bf. The general formula n, -(x), sn (where m = 0) corresponds to the fluorine-containing group lζ represented by =(X)m- (where m = 0 or 1)
Or in the presence of a fluorine-containing thiol represented by 1),
The most preferred method is to radically polymerize a monomer mainly composed of vinyl esters, and then saponify a polyvinyl ester polymer in which an alkyl group or a fluorine-containing group has been introduced at the end by a chain transfer reaction. The detailed method is described below.

The alkylthiols used are Takaken 020.
8fi, c, lower “-” -04M, 8 Hz
r Q 4 H? 8 H1804LBH,%n
061L58H,n CaH+y8H1rt Ql. n
2JH1n 012H2s81i, t 012Hu
8-El, nO+4H, 2g8H1n -C+6Hx3
8■,n (3+aMsySH,n 02ofl(+5
Examples include R1n 024H4t8H, among others n
-C4■q8M, n06tiB13■, n-c8a,,
su, n-0,. H2, Sfi, n-C+2) 125
su, n-0,4H2,8fi, n-0+ bas
5s ■, "C* tJ1575R1n-c2on4
．． aa etc. are very good.

Also, the general formula Ht -fX)m-sii (where m =
As the fluorine-containing thiols represented by 0 or 1),
In the case of m' = 1, what is represented by B, -X-8fi is specifically shown as H(-OF,) 0H20(0fi2-j 811, H
Published F29 CH2O Published H2Fi, 5R1H Published F, Kuan
2o (aa2)5sn, H(OF2901120 (
Ofi,,)31.

F (OF,), 01120 (0H2)58LL%
F<CI!゛2) 5C1-120 (CH2), 5
i-i.

F (OF,), CH20 (CH,) 511F (OF2)
, C1-120(ell2)58LL.

F (OFg)6C1(2CI(z8H1FCOF2
), Cn2an, su, F(OF2)80ff20R
281(,i*°(cx2), using 0H21111
n, F (OF 2 ) + ooit□ah28 M
%F CCF2) a (L River) 8 El, OF. F:>0F-0-(CF2), 2cu2cH28mF
(Of'2)8CH,OR,N-(-01(2 pieces 80.
(1°F(Off'2), 8C■201(28H%F(OF2)
),. 5 (3H20H28EI.

f” (OF2)80ti20)1.S (OH2)
5SR1F (0F2)8-sen2an2ocu2c
u2su, F (OF2)8Son2CH280H2C
H28H1F(C1”2)30ONHCH2(Ai2
8K, F C0F2), 0OHHOki20■28H.

υ etc. can be mentioned.

In the case of m-ro, examples include those shown in kit-81-1.

(among the above fluorine-containing thiols tH-cr2)-c2-OnCH29SUH,,GC
F2 people 0H2-0+On2 people 8H! 11~ [OF2% Off, -0-(OH2→38HF+OF
2+y(an2-+, o bear H2% 8fiF+OF,)
, Oume α bear H2% 81 (irHp, Yaan2s0÷a
■Mountain 8H F GeF4-+80ONIi+C1 (2) Tsu etc. are particularly good batting methods.

/'7/·' Further, any vinyl ester that can be radically polymerized can be used. Examples include vinyl formate, vinyl acetate, vinyl propionate, vinyl persate, vinyl laurate, vinyl stearate, etc.
Among them, vinyl acetate has the best polymerizability and is preferred.

Haladical polymerization initiator for polymerization of vinyl monomers mainly consisting of vinyl esters such as vinyl acetate in the presence of alkylthiols or fluorine-containing thiols (hereinafter both may be abbreviated simply as thiols) In the presence of
Any method such as bulk polymerization, solution polymerization, pearl polymerization, or emulsion polymerization can be used, but solution polymerization using methanol as a solvent is industrially most advantageous.

There are no particular restrictions on the amount of thiols to be added to the polymerization system and the method of addition, and these should be appropriately determined depending on the physical properties of the intended polyvinyl alcohol polymer. As the polymerization method, known methods such as a batch method, a semi-continuous method, and a continuous method can be employed.

As the radical polymerization initiator, known radical polymerization initiators such as 2.2'-azobisisobutyronitrile, benzoyl peroxide, and carbonate peroxide can be used, but 2.2'
- Azo initiators such as azobisisobutyronitrile are easy to handle and convenient to use. Furthermore, radiation, electron beams, etc. can also be used. It is preferable to adopt an appropriate polymerization temperature depending on the type of initiator used, but it is usually 30 to 90℃.
'C selected from the range. After polymerization for a predetermined period of time, unpolymerized vinyl esters are removed by a conventional method to obtain a polyvinyl ester polymer having an alkyl group or a fluorine-containing group at the end.

The polyvinyl ester polymer thus obtained is saponified by a conventional method, but it is usually advantageous to convert the polymer into an alcohol solution, particularly a methanol solution. Not only anhydrous alcohols but also alcohols containing a small amount of water can be used depending on the purpose, and organic solvents such as methyl acetate and ethyl acetate may be optionally contained. The saponification wetness is usually selected from the range of 10 to 70'C. As the saponification catalyst, alkaline catalysts such as sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, etc. are preferable, and the amount of the catalyst used is determined as appropriate depending on the degree of saponification and water content, etc. 0.001 or more in molar ratio to, preferably [3]
．． It is desirable to use 002 or more. On the other hand, if the amount of alkali is too large, it will be difficult to remove the residual alkali from the polymer and the polymer will be colored, which is undesirable, so it is preferable to keep the molar ratio to 0.2 or less.

Through this saponification reaction, a PVA-based polymer containing an alkyl group or a fluorine-containing group at the terminal is obtained, and the PVA-based polymer in the present invention is defined as having a vinyl alcohol unit content of 20 mol% or more, preferably 50 mol% or more, More preferably, it refers to a polymer containing 60 mol% or more, including other monomer components (such as vinyl acetate, vinyl formate, vinyl propionate, vinyl persate, ethylene, propylene, (meth) Acrylic acid and its salts, itaconic acid, maleic acid, fumaric acid and their salts, 2-
There is no problem in containing acrylamide propane sulfonic acid and its salts, (meth)acrylamidopropyltrimethylammonium chloride, and the like. The degree of polymerization is not particularly limited as long as it is in the range of 10 to 6000, but the most effective when used in the present invention are a degree of saponification of 60 to 100 mol% and a degree of polymerization of 100 to 6000.
It is a 0-mouth PVA-based polymer.

PV having an alkyl group or a fluorine-containing group at the terminal of the present invention
In addition to the A-based polymer, other polymeric substances such as PVA-based polymers other than those used in the present invention, gelatin, glue, etc. may be used in combination.

In addition, in the photosensitive resin composition of the present invention, which is characterized by containing a PVA polymer having an alkyl group or a fluorine-containing group at the end and a photosensitizer, the photosensitizer is used in combination with the PVA polymer. The photosensitive resin composition can be made insoluble in water by irradiation with light such as ultraviolet rays, and specifically, dichromate, tetrazonium salt, diazide compound, diazo resin, etc. It can be photopolymerized alone or as a mixture, or in the presence of a photopolymerization initiator such as alkyl ether of benzoin, bromoacetophenone, α-bromoisobutyrophenone, etc., to form a high polymer. Monomers, such as esters of acrylic acid or methacrylic acid of lower alkanols having one or more hydroxyl groups, or esters of acrylic acid or methacrylic acid of polyethylene glycol etherified or esterified on the 10,000 side, or intramolecular Examples include mixtures with acrylamide or methacrylamide derivatives having at least one free hydroxyl group and a photopolymerizable double bond.

These photosensitizers are preferably water-soluble compounds, and are preferably compatible with the PVA polymer having an alkyl group or a fluorine-containing group at the end.

Preferred photosensitizers include ammonium dichromate, sodium dichromate, potassium dichromate,
or diphenylamine-4-diazonium chloride.
Diazo resins such as formalin condensation resin, dimethylaniline-4-diazonium chloride/formalin condensation resin, 2,5-dimethoxyphenylmorpholine-4-diazonium zinc chloride double salt/formalin condensation resin, 5,3-dimethoxydiphenyl-4,4 - Vinudiazonium chloride M lead chloride compound tM,s,s-diethyldiphenyl-4,4
'-bisdiazonium chloride zinc chloride double salt, diphenyl-4,4-bisdiazonium chloride subaluminous chloride double salt,
N-Ethyl-N-benzylaniline-4-diazonium chloride zinc chloride double salt, N-dimethylaniline-4-cyabunium chloride, 3.3-dimethoxydiphenyl-4,4-bisdiazonium chloride, 3.3- Tetrazonium salts such as dimethoxydiphenyl-4,4-bisdiazonium sulfate, diazonium salts, 6-azido-2-(4-azidostyryl)benzimidazole, 4
．． Diazide compounds such as 4-diazidostilbene-2,2-disulfonamide, or benzoin, benzoin methyl ether, benzoin ethyl ether, α-methylbenzoin, bivaloin, anthraquinone, 1-chloroanthraquinone, 2-methylanthraquinodi, ω -bromoisobutyrophenone, α-bromoisobutyrophenone, 1
．． A photopolymerization initiator such as 4-naphthoquinone, and a photopolymerizable monomer that is miscible with the PVA polymer, such as ethylene glycol acrylate, ethylene glycol methacrylate, ethylene glycol dimethacrylate, triethylene glycol methacrylate, polyethylene glycol dimethacrylate. methacrylate, β-oxydipropyl methacrylate, and N-β-oxyethylacrylamide, N-
Oxymethylacrylamide, N,N-bis(β-oxyethyl)acrylamide, N-α,α-dimethyl-β
-At least one selected from oxydiethylacrylamide, N-γ-oxypropylacrylamide, N-p-oxyphenylacrylamide, N-β-oxyethyl-N-methylacrylamide, and methacrylamide derivatives corresponding thereto. Examples include mixed systems with monomers, etc.

Among the above photopolymerizable monomers, ethylene glycol methacrylate, ethylene glycol dimethacrylate, N-β-oxyethylmethacrylamide, N,N-
Bis(β-oxyethyl)acrylamide, and N-α
, α-dimethyl-β-oxydiethylmethacrylamide is particularly preferred.

Further, a part of the above-mentioned photopolymerizable monomer may be replaced with a conventionally known photopolymerizable monomer, such as acrylamide or methacrylate, within a range that does not impair the object of the present invention.

There is no problem in substituting with amide, m-xylene bis-acrylamide, p-xylylene bis-methacrylamide, m-phenylene bis-acrylamide, ethylenediamine bis-acrylamide, hexamethylene diamine bis-methacrylamide, and the like.

PV having an alkyl group or a fluorine-containing group at the terminal of the present invention
In a photosensitive resin composition characterized by containing an A-based polymer and a photosensitizer, the amount of the photosensitizer added to the PVA-based polymer is as follows: When the photosensitizer is a dichromate, Agent 1 PVA polymer (weight ratio) -01/1o.

~20/100 is preferable, more preferably 1/100~10/
100 is especially good for punching.

When the photosensitizer is a tetrazonium salt, diazide compound, diazo resin, etc. alone or in a mixture, photosensitizer/PVA polymer (weight ratio) = 1/10 to 50
/100 is punching, and even 5/100 to 20/100
is particularly preferred.

When the photosensitive agent is a mixture of a photopolymerization initiator and a monomer that can be photopolymerized to form a high polymer in the presence of the photopolymerization initiator, the photosensitive agent/PVA polymer (weight ratio) = 30/ 100-4
00/100 is preferable, more preferably 50/10~
A special number of 500/10 is preferable.

In the photosensitive resin composition of the present invention, in addition to the above-mentioned photosensitizers, known sensitizers such as uranyl acetate compounds can be appropriately used in combination. Further, additives such as plasticizers, dispersants, antifoaming agents, etc., phosphor particles in the case of making a phosphor screen for television cathode ray tubes, pigments, etc. in the case of photocurable paints are added as necessary. In addition, a known thermal polymerization inhibitor or storage stabilizer may be included for the purpose of improving storage stability.

The photosensitive resin composition of the present invention will be specifically explained below, but the present invention is not limited to these Examples in any way. Note that parts and % indicate parts by weight and % by weight unless otherwise specified.

/'/' 2・/ Example 1 Has nCl2H25 group at the end, average degree of polymerization 1500
An aqueous solution containing 3% polyvinyl alcohol (hereinafter abbreviated as PVA) with a saponification degree of 87.5 mol% and ammonium dichromate adjusted to 3% relative to the PVA was applied onto a galanu board to a thickness of 12 μm. It was applied as a film and dried. Next, the line drawings were placed in close contact in a vacuum printing frame, exposed for 60 seconds using a 2000 lux chemical lamp as a light source, and developed with water. Table 1 shows the performance of the obtained photosensitive plate.

Also, for comparison, instead of the above-mentioned terminal-modified PVA,
Ordinary unmodified PVA (polymerization degree 1700, saponification degree 89
A photosensitive solution was prepared in the same manner as in Example 1 above, except that mol %) was used, a photosensitive plate was obtained, and its performance was evaluated. The results are shown in Table 1 as Comparative Example 1.

From the comparison between the two, it was found that the t' photosensitive resin composition containing 6PVA having an n-Cl2H2S group at the terminal of the present invention was immediately photosensitive. PV) having an average polymerization degree of 1560 and a saponification degree of 88.2 mol%
A photosensitive solution prepared by adding 1 part of diphenylamine-4-diazonium chloride formalin condensation resin to 100 parts of a 10% aqueous solution of A was coated uniformly on a zinc plate using a rotary coater, dried, and then the line drawing was baked in a vacuum. Closely fit in the frame 2
The film was exposed to light for 3 minutes using a 000 lux chemical lamp as a light source, and then developed with water. The obtained image plate is immersed in a 5% chromic acid aqueous solution for 30 minutes to perform hardening treatment, and then burned at 120° C. for 10 minutes to obtain an acid-resistant image resist. This was rubbed with 10% sulfuric acid in a conventional manner to remove the skin, and then subjected to dow etching to obtain a printed image for a relief board. Table 2 shows the performance of the obtained photosensitive plate.

For comparison, in addition to the above-mentioned terminal-modified PVA wire,
Ordinary unmodified PVA (polymerization degree 1700, saponification degree 89
A photosensitive solution was prepared in the same manner as in Example 2 above, except that mol %) was used, a photosensitive plate was obtained, and the performance was evaluated, which is shown in Table 2 as Comparative Example 2. From the comparison of the two, it is clear that H at the end of the present invention
It can be seen that the photosensitive resin composition containing PVA having (CF2)CH2-0 (CH2% group) has excellent photosensitivity and can provide clearer images.

Examples 3 to 6 A photosensitive solution was prepared under the same conditions as in Example 2, except that various end-modified pvm shown in Table 3 was used instead of PVA having HCCF2AoCH20 (CH2 group) at the end of Example 2. ,
A photosensitive plate was obtained by exposure and development. Table 3 shows the type of PVA and the performance of the photosensitive plate.

Example 7 H(CFz)rCH2-0-(CH2
Instead of PVA with i group, n-Cl2H2 at the end
It has an S group, an average degree of polymerization of 350, and a degree of saponification of 88.3 mo/
A photosensitive solution was prepared under the same conditions as in Example 2 except for using a mixture of 50 parts of PVA with 50 parts of conventional unmodified PVA (average degree of polymerization 2000, degree of saponification 88 mol%), exposed and developed. A photosensitive plate was obtained. Table 4 shows the type of PVA and the performance of the photosensitive liquid.

Table 4

Claims (4)

[Claims] (1) A photosensitive resin composition characterized by containing a polyvinyl alcohol polymer having an alkyl group or a fluorine-containing group at its terminal and a photosensitizer. (2) The photosensitive resin composition according to claim 1, wherein the alkyl group has 2 to 24 carbon atoms. (3) The photosensitive resin composition according to claim 1, wherein the alkyl group has 4 to 20 carbon atoms. (4) The photosensitive resin composition according to claim 1, wherein the fluorine-containing group is represented by the general formula R_f-(X)_m- (where m=0 or 1). [Here, R_f represents a fluorinated alkyl group represented by the following formula [1], or a fluorinated alkyl ether group represented by the following formula [2] or [3]. A-(CF_2)-_q...[1] (However, q=2-20, A=H or F or ▲There are mathematical formulas, chemical formulas, tables, etc.▼or ▲There are mathematical formulas, chemical formulas, tables, etc.▼) ▲ There are mathematical formulas, chemical formulas, tables, etc.▼...[2] (However, q = 2 to 20) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[3] (However, t = 1 to 10) Also, X is An alkylene group represented by the following formula [4], [5
] An alkylene ether group represented by the formula [6], an alkylene amide group represented by the formula [7], an alkylene lentioether group represented by the formula [8], an alkylene imiso group represented by the formula [9] or [10] Indicates any one type of alkylene ester group represented by the formula. -(CH_2)-_n...[4] (However, n=1 to 5) -(CH_2)-_pO-(CH_2)-_n...[
5] (However, p = 1 to 5, n = 1 to 5) -CONH- (CH_2) -_n...[6] (However, n = 1 to 5) -(S)_r- (CH_2)-_pB- (CH_2)-
...[7] {However, p = 1 to 5, n = 1 to 5, B = sulfur atom or oxygen atom (however, when B = sulfur atom, r = 0 or 1, B =
When it is an oxygen atom, r = 1)} ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [8] (However, p = 1 to 5, n = 1 to 5, R_1 = C_1 to C_
5 alkyl group) -(CH_2)-_pCOO-(CH_2)-_n...
・[9] (However, p = 1 to 5, n = 1 to 5) -COO-(CH_2)-_n... [10] (However, n = 1 to 5)]