JPS58164603A - Production of self-sensitizing photopolymer - Google Patents

Abstract

PURPOSE:To obtain a self-sensitizing photopolymer showing good photocurability, by reacting a copolymer having a halogenoalkyl group and a sensitizer unit on a side chain with a photosensitive group-containing compound reactive with a halogenoalkyl group. CONSTITUTION:A copolymer having a halogenoalkyl group and a sensitizer unit on a side chain is prepared either by copolymerizing a halogenoalkyl group- containing monomer (e.g., chloromethylstyrene) with a sensitizer unit-containing monomer (e.g., N-(p-nitrophenyl)acrylamide) or by reacting a polymer containing a halogenoalkyl group on a side chain with a sensitizer unit-containing compound reactive with a halogenoalkyl group, e.g., gamma-nitrophenol. The purpose self-sensitizing photosensitive resin is obtained by reacting the copolymer with a photosensitive group-containing compound reactive with a halogenoalkyl group, e.g., acrylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a self-sensitized photosensitive resin. Furthermore, a self-sensitizing photosensitive resin OIl made of a copolymer having a photosensitive group and a sensitizer unit in the side chain, respectively.
Manufacturing method K11.

A self-sensitizing lidded photosensitive resin consisting of a copolymer bonded by a photosensitive group consisting of a cinnamate ester group and an acid amide group, each flanked by a sensitizer unit, was previously developed by the present inventor. One object of the present invention is to provide a method for producing such a self-sensitized photosensitive resin, which has been proposed (see Japanese Patent No. 111855-'LR-623). Another object of the present invention is to provide a method for producing a self-sensitizing photosensitive resin having a photosensitive group other than a cinnamic acid ester group in its side chain. The object of the present invention is to provide a method for producing a self-sensitizing photosensitive resin O having a sensitizer unit other than the sensitizer unit bonded by an ad group in its side chain.

In the method for producing a self-sensitized photosensitive resin according to the present invention, a photosensitive group-containing compound capable of reacting with the halogenoalkyl group is reacted with a copolymer each having a halogenoalkyl group and a sensitizer unit in the side chain. It consists of causing

Eight day Genoalkyl J on 1Ill chain? Copolymer having 7 halogenoalkyl group-containing monomers and a sensitizer unit Kofun monomer,
Alternatively, by reacting a homopolymer or a comonomer containing a halogenoalkyl group with a polymer having a halogenoalkyl group in the side chain, a compound containing a sensitizer unit that can react with the halogenoalkyl group. Obtainable.

Examples of the halogenoalkyl group-containing monomer include hachloromethylstyrene, 2-tetraethyl vinyl ether, and
-chloroethyl acrylate t2-chloroethyl methacrylate, vinyl chloroacetate, epichlorohydrin, bischloromethyloxetane, and the like. Examples of the sensitizer unit-containing monocylindrical body copolymerized with these 710 genoalkyl group-containing monomers include N-(p-nitrophenyl)acrylic acid iY, N-(p-nitrophenyl)methacrylamide, N- -(4-nitro-1-naphthyl)acrylamide, N-(4-nitro-1-naphthyl)methacrylamide, ni-acryloyloxy-N-1'(p
-nitrophenyl)acetamide, 1-meth'□ri, lyloyloxy-N-(p-nitrophenyl)acetand, l-acryloyloxy-
H-(4-di-a-1-su7tyl)acetamide, 1-
Examples include condensation reaction products of methacryloyloxy-)i-(4-nitro-1-naphthyl)acetoand, benzoin-chloroacetyl chloride condensate and acrylic acid, and alkali metal salts of methacrylic acid. The copolymerization reaction between these monomers is generally carried out in an aprotic polar solvent such as dimethylformamide or hexamethylphosphoramide, but there is no limitation to this solvent as long as the copolymerization reaction is carried out. It's not a thing.

When a polymer having a halogenoalkyl group in the side chain is used, a homopolymer of the above-mentioned halogenoalkyl group-containing monomer, a mutual copolymer thereof, or various monomers having no halogenoalkyl group with these monomers. 1 in copolymer with body
A compound containing a sensitizer unit that can react with the halogenoalkyl group in these polymers is reacted. Such sensitizer unit-containing compounds include p-ditrophenol, di-4-dinitrophenol, 4-nitro-dinaphthol, dinitro-dinitron-naphthol, p-2)a benzoic acid,
-(2-carboethoxy)anthraquinone, 1-carboxyiichiban-nitronaphthalene.

Alkali metal salts and ammonium salts of compounds obtained from Tonanashi 1
Alternatively, in the 8 reaction in which biclatrate, methylnione, etc. are used, an aprotic polar compound such as dimethylformamide, hexamethylphosphoramide, etc. is reacted in the presence of a quaternary ammonium salt such as tetra(n-butyl)ammonium bromide, Although it is generally carried out in a solvent, as long as the condensation reaction is carried out, there are no limitations on the presence or absence of this catalyst, the amount used, the solvent Os, and the amount used.

A photosensitive group-containing compound capable of reacting with the no-lognoalkyl group in this copolymer is reacted with the copolymer obtained by K in this way, which has a no-a-genoalkyl group and a sensitizer unit in the side chain, respectively. By doing so, a self-sensitized photosensitive resin OII is produced. Examples of the photosensitive group-containing compound include acrylic acid, methacrylic acid, crotonic acid, sorbic acid, cinnamic acid, p-(2-benzoylvinyl)benzoic acid fa
t,p-(g-penzoylvinyl)cinnamic acid,! -styrylacrylic acid, a-cyano-! - Alkali metal salts or ammonium salts of carboxylic acids having a photoreactive unsaturated bond in the molecule, such as styrylacrylic acid, cinnamylidenepyruvic acid, α-cyano-cinnamylidenepyruvic acid, etc.
Furthermore, metal azides such as sodium azide and potassium azide are used, and these undergo a condensation reaction with the halogen atoms of the halogenoalkyl groups in the copolymer. The condensation reaction is carried out in the presence of a catalyst such as a quaternary ammonium salt such as tetra(n-butyl)ammonium bromide or a tertiary amine, an aprotic polar solvent such as dimethylformamide, hexamethylphosphoramide, or an inert solvent such as toluene. The condensation reaction is generally carried out in an active solvent, but is not limited to these catalysts and solvents.
．． .

A sensitizer unit-containing compound that can react with a copolymer having a halogenoalkyl group and a sensitizer unit in the side chain, and a sensitizer unit that can react with a polymer having a halogenoalkyl group in the side chain 5 and a sensitizer unit, respectively. When obtained by reaction with a photosensitive group, this reaction can be followed by a reaction on a photosensitive group-containing compound in the same reaction system.

In the resulting self-sensitized photosensitive resin, it is preferable that the sensitizer unit is present in a proportion of about 2 to 50 mol%, and that the photosensitive group is present in a proportion of about 50 mol% or more. The relative proportions of sensitizer units and photosensitive units range from about 3 to 5 O
mol%, preferably about 6-80 mol%, about 98-50 mol%, preferably about 95-80 mol% of 119 photosensitive groups
, and generally a photosensitive resin having a sensitizer unit and a photosensitive group in the inner chain of the molecule in such a proportion is capable of efficient energy transfer from the sensitizer unit to the photosensitive group. As a result, a photosensitive resin prepared by adding a low molecular weight sensitizer to a copolymer having only photosensitive groups shows good photocurability at or above f151i. Therefore, the stain-enhancing, sensitizing resin of the present invention exhibits such good photocurability, and also maintains ML properties and works in the exposure process 11. In terms of preventing the deterioration of the soil, it is also effective in eliminating the defects that occur when low molecular weight sensitizers are used.

Next%l! The present invention will be explained with reference to examples.

Reference Example 1 Chlormethylstyrene 4SL49II (α31861!
mol) and 1-methacryloyloxy-N-(4-nitro-1-naphthyl)acetamide &9611 (α0126
mol) was dissolved in dimethylformamide 60BgK, and azobisisobutyronitrile α4 was added as a polymerization initiator to this.
'F7jl (00029 mol) was added and copolymerized in a nitrogen stream at 60°C for 6 hours and then at 80°C for 1 hour. The resulting polymer solution was poured into methanol to precipitate the copolymer. Let me do it, 1! It was reprecipitated three times with tetrahydrofuran-methanol and purified.

The obtained copolymer was 2a74j (yield 6α03%),
The viscosity of this sp/c (05I/dj dimethylformamide, 80°C) is α10, and the copolymerization ratio of sensitizer units in the copolymer is good as determined from the halogen analysis value.

Reference Example 2 In Reference Example 1, chloromethylstyrene 4SL051
Using F(all'F611-t-l), l-methacryloyloxy-N-(4-nitro-1-naphthyl)acetamide &5511j (00146 mol), azobisin buty-nitrile α4〒6# (α0o29 mol),
A copolymerization reaction was performed.

The obtained copolymer was 8α1Ui (yield 4&16%),
The viscosity ηs p/c of this is α13, and the copolymerization ratio of sensitizer units in the copolymer is a97% to 9%. Reference Example 3 In Reference Example I, l-methacryloyloxy-N-(
4-2) 1-methacryloyloxy-N-(p-nitrophenyl)acetamide instead of a-1-naphthyl)acetamide! Using 04931F (αO(
1 mol) used 1.

Then, a copolymerization reaction was carried out.

The obtained good copolymer was 3αQ81i (yield 6a29%), its viscosity ηap/c was α18, and the copolymerization ratio of sensitizer units in the copolymer was a6 mol %.

Reference side number p-methylsterene l 20 II Wopenzen 160
- and add 1 part of azobisisobutyronitrile to this.
1j was added and polymerized for 8 hours at +60°C in a nitrogen stream. Methanol was added to the resulting nine-polymerized solution to precipitate the polymer, and the polymer was reprecipitated three times with 7cetone-methanol for purification. did. The obtained mourning poly(chloromethylstyrene) was 10Q6jl (yield 91s%), and its viscosity was
8 p/c was αlδ.

Example 1 Copolymer a815# (00221 mol as chloromethyl group) obtained in Reference Example 1 was mixed with N-methylpyrrolidone ao
VK was dissolved, and tetra(n-butyl)ammonium bromide α6661 (α0022 mol) and cinnamate potassium chloride I (αOQδ mol) were added thereto, and the mixture was heated at 60°C.
After the reaction was completed, the reaction solution was poured into water to precipitate the reaction product, which was reprecipitated twice with acetone-water and once with atomyl-methanol, and purified. .

The formed copolymer weighed 91 g (yield: 3%), and its viscosity ηsp/c was αIO, determined from the halogen analysis value, and the reaction rate of the tetramethyl group was 999% or more. 1゜This copolymerization-'11 is converted into 10-cyclohexanone.

Dissolve the solution in **, apply it on the plow board using a spinner, dry it*, *, and apply it with a Kenkar lamp (15Wx'F) for 3 times using Kodak Step Tablet Flat 2.
Exposure for 1 minute from a distance of 51, then 2
Good for a minute.

Examples 2 to 3 The copolymers obtained in Reference Examples 2 to 3 were reacted with potassium cinnamate and measured for the number of insolubilization steps in the same manner as in Example 1.

Comparative Example 1 Nine poly(chloromethylstyrene) obtained from the reference side number was reacted with potassium cinnamate and the number of insolubilization steps was measured in the same manner as in Example 1.

The results obtained in Examples 1-3 and Comparative Example 1 are shown in Table IK.

Table 1 Example 1 'Fa3 919 010
31st stage #2 8Q! 5 z α091 #38Ql # α13 1 Comparative example 1 843 1 #
Good copolymer 1738II (α01 mol) obtained in Reference Example 1 and sodium azide α780j (α01 g mol) were dissolved in dimethylformad, and 322 g of tetra(n-butyl)ammonium bromide α (α001 After the completion of the reaction, the reaction solution was poured into methanol to precipitate the reaction product, and then 1FjA was reprecipitated twice with tetrahydrofuran-water and twice with tetrahydrofuran-methanol. 9.

The formed electrical metal body is 1451231 (yield 90%),
The viscosity ηa p /c of this is α13, and the reaction rate of the chloromethyl group determined from the halogen analysis value is 99.
9% or more - This copolymer was measured for the number of insolubilization steps in the same manner as in Example 1, but the exposure time was extended to 16 minutes.

The copolymer obtained in Example Reference Example 3 was reacted with sodium azide and measured for the number of stages of step insolubilization in the same manner as in the actual feeding.

Comparative Example 2 Poly(phosphorus methyl styrene) obtained in the reference side number was reacted with sodium azide and measured for the number of insolubilization steps in the same manner as in the actual side number.

lI! The results obtained in Example Male Side 5 and Comparative Example 2 are shown in Table 2 below.

Table 2 Example 49 α0 5) Q9 α13 12
Stage l δ G&'F I
Qlδ Stage comparison example 2 9αl
#-1 stage reference example 6 Pe/zoin 2L 226Jl (αIo mol) and pyridine 8
- and benzene 120 sd, - were dissolved, and chloroacetyl chloride 8 m/(a little over 010 moles) was dissolved in this and 10
It is added dropwise at a temperature below 0.degree. C. and reacted as shown in the following equation.

0-CCH agricultural cz (1) After that, it was stirred at room temperature and diluted with a dilute aqueous sodium hydrogen oxide solution.
After washing twice with water and five times with water and drying with anhydrous magnesium sulfate, the oil was recrystallized with cyclohexanone.
One crystal [1] having a temperature of 610 to 616°C was obtained as lQ9911 (yield 6Q5%).

This crystal (1) ILjS49jl (CLO4%), potassium methacrylate a209j (α0δ mol), tetra(n-butyl)ammonium bromide L $! 89j
(0,004 mol) and a small amount of tert-butylcatechol as a polymerization inhibitor were reacted in dimethylformamide, hydrogen, hydrogen for 4 hours at room temperature as shown in the following formula, and the reaction product 12,940 II (Yield 9 to 61%')
, get it.

Margin below CH.

[Seal]

When this is purified by recrystallization with methanol, the melting point is 9λ0.
A crystal of ˜9+iL5° C. was obtained, which was confirmed by its structure line infrared absorption spectrum, NMR spectrum and elemental analysis.

This crystal (1) & 3$1lj (QOO69JEL) and chloromethylstyrene IQ891N (01303 mol) were dissolved in dimethylformamide 40-, and the following Reference Example 1 was prepared.
When a copolymerization reaction is carried out in the same manner as above, the copolymer lLa9sy (
A yield of 52-)%) was obtained, and its viscosity ηsp/c was α
In No. 15, the proportion of sensitizer units in the copolymer determined from the halogen analysis value is ao mol%, which is 9.

Example 6 Essential polymer obtained in Reference Example 6:',, 8 a 6 j
(001 mol) and potassium p-(g-benzoylvinyl)benzoate &904j (001 mol) were dissolved in 20sgK of dimethylformamide, and the mixture was heated to room temperature in the presence of tetra(n-butyl)ammonium butetramite α3229 (α001 mol). After the reaction was completed for 24 hours, the reaction solution was poured into methanol to precipitate the reaction product, and reprecipitation was performed twice with tetrahydrofuran-water and once with tetrahydrofuran-methanol.

The formed copolymer has a reaction rate of 9%, a yield of &F439(yield &S%), and a viscosity ηap/c of α
18 and nine.

Using this copolymer, the same step insolubilization step number q) 11 was carried out as in Leprosy Side 1. However, the exposure time was varied in various ways.

EXAMPLE 2 In Example 6, potassium p-(8-benzoylvinyl)cinnamate was used in place of p(''-benzoylvinyl)benzoic acid, and a similar reaction was carried out. Gasaihiro, reaction rate is 9919%, yield is a09QII
(yield 7a4%), its viscosity ηap/e is αl”F
Met.

Regarding this co-merger, the number of step insolubilization steps is measured in the same manner as in Example 1, except that the exposure time may be varied in various ways.

Comparative Examples 3-4 p-(2-benzoylvinyl)benzoic acid
-benzoylvinyl) cinnamic acid (reaction rate: 989%), the number of steps for insolubilization was measured in the same manner as in Example 1.

The good results obtained in Examples 6-7 and Comparative Examples 3-4 are shown below.

Table 3 Example Exposure time Step insolubilization step number Example 6 30 seconds 6RI
1 minute 9 stages l g minutes
, 111IR Example 7 10 seconds 14
Stage...--l, l 30 seconds 19R 11 minutes 21R Comparative Example 3 y 6-stage Comparative Example 4 # 16-stage Example 8 Nine poly(chloromethylstyrene) obtained in Reference Example 4 L5
ja6j (001 mol) methylformamide goW
IIK was dissolved, and tetra(n-butyl)ammonium bromide α313j (0001 mol) and p-nitrophenol potassium salt αoss' (α0005 mol) were sequentially added to the kernels, and the mixture was allowed to react at room temperature for 24 hours.
Add 1862 g (001 mol) of potassium cinnamate,
After completion of the reaction, which was further reacted for 24 hours at room temperature, the reaction mixture was poured into 300 g of water to precipitate the reaction product, and then reprecipitated with acetone-water 8 times and acetone-methanol once.

The amount of good copolymer formed was 12,517 g (yield 465%), its viscosity ηgp/c was α44, and as a result of NMR spectrum and elemental analysis, this copolymer contained ゛ photosensitive -9B mol. % and sensitizer units of 6 mol % J
,, 10 copies] It was confirmed that 11□ of each comonomer component was formed at an O ratio.

Regarding this copolymer, the step number insolubilization was measured in the same manner as in Example 1. However, the exposure time could be extended to 3 minutes.

Example 9 The same reaction as in Example 8 was carried out by changing the amounts used of potassium salt of p-latrophenol to α53$ag (α003 moles) and potassium cinnamate to 13964F (αQO'75 moles). mourning, the copolymer formed is L
It was confirmed that F811I (yield 6a1%) had a viscosity ηsp/c of α3, and that 30 mol% of sensitizer units were present therein.

Regarding this copolymer, the same step number of insolubilization steps as in Example 8 was measured.

Example 10 In Example 8, potassium # of p-nitrophenol
Similar reactions were carried out by changing the Kfi doses of A to αasajl (αooa mole) and potassium cinnamate to LO24j (QOOISB% le). Formed material polymer 1i
L949JF (yield 1b%), and its viscosity ηap/c was α25.

For the and Φ copolymers, the step number of insolubilization stages O1l was determined in the same manner as in Example 8.

The nine results obtained in Examples 8-1o are shown in Table 4 below. In addition, as Comparative Example 5, the III constant results for an exposure time of S minutes for a homopolymer of cinnamate ester (reaction rate 999%) obtained by reacting poly(chloromethylstyrene)K potassium cinnamate were shown. Also listed in 9.

Table 4 Example 8 9R I 9 Iz 10
1i1jj Comparative Example S 0-stage Example 11 In Example 8, potassium salt of p-nitrophenol was substituted with potassium p-nitrobenzoate α20δICα0
Potassium cinnamate was added to L flo81 using
(00095 mol) and reacted in the same manner. The copolymer formed was: taja5+ (yield 6L'F%),
Its viscosity v) mp/c is α31, in which it is assumed that 10 mol% of sensitizer units are present.

Regarding this copolymer, when the number of step insolubilization steps was measured in the same manner as in Example 8, it was 9, which was 2 steps.

Example 18 In J[II, the potassium salt of 2-carbohedipenzophenone α226jl (α001 mol) was substituted for the potassium salt of p-nitrophenol, and DK potassium crotonate L180j (α009
5 mol) of each can be used. The formed copolymer was L894jl (yield 8Q1!%) and its viscosity qa
It can be confirmed that the p/c is α16 and that 10 mol% of sensitizer units are present therein.

When the number of steps of insolubilization of this copolymer was measured in the same manner as in Example 1, it was found to be 1 step.

Comparative Example 6 , ′: Po.

Reference Example 4 9 Poly(chloromethylstyrene) 16
26j (α01 mol) and potassium crotonate L303j
(α0106 mol) was reacted in the same manner as in Example 12, and the number of step insolubilization steps in the same manner as in Example 1 was measured for the good copolymer formed, which was 0 steps.9.

Example 13 In Example 8, the potassium salt of p-nitrophenol (K) tyleomine 06841 (0001 mol) was substituted with potassium cinnamate (Ka-cyano!). - Potassium styryl acrylate &ji54# (0009154
) were used respectively. A good copolymer formed is L3
221 (yield 64-3%), and its viscosity ηap/c is α
It was confirmed that 10 mol% of sensitizer units were contained therein.

Similarly, poly(chloromethylstyrene) and α-amino-
Reaction with potassium β-styrylacrylate:・::.

The reaction rate was 9% (9%), and its sensitivity and photoreactivity were 1: ◆.

Using a step tablet, no difference was observed between the two, and in good condition, ultraviolet rays based on 1α-cyano-β-styryl acrylic acid ester groups were detected by cutting off the liquid length of 400 W or less using a filter. We measured the decrease in the absorption spectrum and found that in the latter case, no decrease in the spectrum was observed after 10 minutes of irradiation with ultraviolet rays, whereas in the former case, a slight decrease in the spectrum was observed, indicating that α-cyano- It was confirmed that energy transfer to the I-styryl acrylate group occurred and molecular sensitization was achieved.

agent Patent attorney Tomio Yoshida

Claims (1)

[Scope of Claims] Self-sensitization characterized in that a copolymer having a halogenoalkyl group and a sensitizer unit in the side chain, respectively, is reacted with a photosensitive group-containing compound capable of reacting with the halogenoalkyl group. Type photosensitive resin OII manufacturing method. Claim 1, in which a copolymer of a halogenoalkyl group-containing monomer and a sensitizer unit-containing monomer is used as the copolymer having a halogenoalkyl group and a sensitizer unit in the λ side chain, respectively. A method for producing a self-sensitized photosensitive resin as described in Section 1. & A reaction product of a polymer having a halogenoalkyl group and a sensitizer unit-containing compound capable of reacting with the halogenoalkyl group, as a copolymer having a halogenoalkyl group and a sensitizer unit in the side chain, respectively. A method for producing a self-sensitizing photosensitive resin according to Section 1 of Claims I, in which the following is used. The self-sensitizing photosensitive resin according to claim 3, in which a copolymer of chloromethylstyrene is used as the co-electronic polymer having a halogenoalkyl group in the side chain. The self-sensitizing type according to claim 1, wherein a carboxylic acid salt having a reactive unsaturated bond in the molecule is used as the photosensitive group-containing compound capable of reacting with the Δhalogenoalkyl group. Method for producing a photosensitive resin. d. A method for producing a self-sensitizing photosensitive resin according to Claim 1, Paragraph 1, in which a metal azide is used as the photosensitive group-containing compound capable of reacting with a halogenoalkyl group.