JPS61236805A - Functional polymer - Google Patents

Abstract

PURPOSE:To provide a novel polymer of high performance in adhesivity, photosensitivity, radiation sensitivity and radiation resistance, useful as an adhesive especially for copper surface, having at its side chain, such functional groups as benzotriazole, nitroaryl or chloroaryl one. CONSTITUTION:For example, (A) a side chain epoxy group-contg. pohymer of formula I (n is 1-10,000; PGMA is polyglycidyl methacrylate) and (B) a substituted benzoate of formula II [R1 is nitro or halogen; R2 is alkyl, (nitro, halogen-substituted)aryl, aralkyl, benzotriazole, benzoxazole or benzothiazole; X is O or S] are brought to addition reaction in the presence of, e.g., a quaternary ammonium salt, to obtain the objective novel polymer having recurring unit of formula III {e.g., poly[2-benzoyloxy-3-(1-benzotriazolyloxy)propyl methacrylate]}.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to functional polymers, particularly novel adhesive, photosensitive, radiation sensitive, and radiation resistant polymers.

Polymers containing point side chain epoxy groups are widely used as raw materials for the synthesis of functional and crosslinkable polymers.
The present inventors conducted an addition reaction between a side chain epoxy group in a glycidyl methacrylate (GMA) copolymer and a photoreactive carboxylic acid using a quaternary ammonium salt as a catalyst.
Obtaining a photosensitive polymer [Kobunshi Papers Vol. 32, No. 6
04 page (1975)), and recently, the inventors have
and the side chain epoxy group in the methyl methacrylate copolymer and 4-nitrophenyl cinnamate etc. are subjected to an addition reaction using a tertiary amine and a quaternary ammonium salt as a catalyst,
It has been proposed to obtain a self-sensitizing photosensitive resin (Japanese Unexamined Patent Publication No. 59-216138).

Although these resins are excellent as photosensitive resins due to the photodimerization reaction of the cinnamate ester in the side chain, they have no effect on other properties such as adhesion, sensitivity, radiation sensitivity, and radiation resistance. .

. In order to achieve this, the present inventors further investigated the addition reaction products of side chain (pendant) epoxy group-containing polymers and esters.
By selecting benzoates containing thiobenzoxazole groups, they differ from reaction products with cinnamic acid or cinnamate esters.

Adhesion, photosensitivity due to nitro and chloro groups,
The present invention was achieved by discovering that it is possible to produce a new polymer having radiation sensitivity or radiation resistance due to the sulfur element.

That is, the present invention relates to a functional polymer having a repeating structure represented by the following general formula, where n is 10 to 10,000°, X is ○ or S, R5 is a nitro group or a halogen group, and R2 is an alkyl group. group, an aryl group, an aralkyl group, a nitro group or a halogen-substituted aryl group, a benzotriazole group, a benzoxazole group, a benzothiazole group.

In R2 above, the alkyl group is methyl, ethyl group, isobutyl group, tart-butyl group, chloromethyl group, trichloromethyl group, fluoromethyl group, bromomethyl group, benzyl group, etc., and the nitro group-substituted aryl group is 4-
Nitrophenyl, 2-nitrophenyl, 2,4-dinitrophenyl, 2.4.6-dolinitrophenyl, 2,4
-dinitrophenyl, 4-nitronaphthyl, 2-nitronaphthyl groups, etc., and halogen group substitutions include 4-chlorophenyl, 2,4-dichlorophenyl, 2,4゜6-dolichlorophenyl, 2-chlorophenyl, 3-chlorophenyl, 2,5-dichlorophenyl, 4-chlorophenyl,
4-bromophenyl, 4-iodophenyl, 2,4-dichlorophenyl, 2-chloronaphthyl, 2,4-dichloronaphthyl.

2,6-dichloronaphthyl, 2,4-difluoronaphthyl, and the like.

The high molecular weight polymer of the present invention is produced by subjecting a side chain epoxy group-containing polymer represented by the following formula to an addition reaction with a substituted benzoate.

CH3 (CH2-C柘- ■ CH3 (where n is 10 to 10,000, preferably 100 to
toooo, and X, R, and R2 are the same as above) Examples of the side chain epoxy group-containing polymer include homopolymers or copolymers such as glycidyl acrylate, allyl glycidyl ether, p-vinylphenyl glycidyl ether, etc. It will be done. In the case of a copolymer, methyl acrylate, ethyl acrylate, butyl methacrylate, styrene, vinyl acetate, N-vinylpyrrolidone, etc. are copolymerized in a proportion of about 80 mol% or less, preferably about 55 mol% or less. .

The viscosity (or molecular weight) of the side chain epoxy group-containing polymer in the present invention, for example, polyglycidyl methacrylate (PGMA), can be determined by changing the initiator concentration, monomer concentration, polymerization temperature, etc. during radical polymerization of glycidyl methacrylate (GMA). From a practical standpoint, n = 10 to 10,000, preferably 10 to 100.
It has a degree of polymerization of 00.

Examples of substituted benzoates include 1-penzotriazolylbenzoate (2a), 2-benzoxazoylthiobenzoate (2b), 2-benzothiazolylthiobenzoate (2c), and 4-nitrophenylbenzoate (2a).
2d), phenylthiobenzoate (2e), 4-nitrophenyl-4-nitrobenzoate (2f), 2-nitrophenylbenzoate (2j), 2,4-dinitrophenylbenzoate (2k), 4-chlorophenylbenzoate (21) , 2,4-dichlorophenylbenzoate (20), phenyl 4-nitrobenzoate (2
q), benzotriazole group, nidroaryl group in the molecule such as phenyl 4-chlorobenzoate (2r).

Examples include benzoates containing a chloroaryl group or an elemental sulfur.

These benzoates are prepared by reacting the corresponding benzoyl chlorides with phenols.

The novel polymers obtained according to the present invention are, for example, poly[2-benzoyloxy-3-(1-benzotriacylyloxy)propyl methacrylate] (3a), poly[2-benzoyloxy-3-(2-penzoyloxy) zolylylthiooxy)propyl methacrylate) (3b)
, poly[2-benzoyloxy-3-(2-benzothiazolylthiooxy)propyl methacrylate l(3e)
, poly[2-benzoyloxy-3-(4-nitrophenoxy)propyl methacrylate) (3d), poly[2
-benzoyloxy-3-thiophenoxypropyl methacrylate) (3a), poly[2-benzoyloxy-
3-(4-chlorophenoxy)propyl methacrylate,
.

(31), poly(2-(4-nitrobenzoyloxy)-3-phenoxypropyl methacrylate) (3q
), poly(2-(4-nitrobenzoyloxy)-3-
(4-nitrophenyl)propyl methacrylate) (3
・f), poly(2-benzoyloxy-3-methoxypropyl methacrylate) (3 g), poly[2-benzoyloxy-3-ethoxypropyl methacrylate) (3
h), poly[2-acetoxy-3-phenylpropyl methacrylate) (3i).

Poly[2-benzoyloxy-3-(2-nitrophenyl)propyl methacrylate] (3j), poly[2-
Benzoyloxy-3-(3,4-dinitrophenyl)
(propyl methacrylate) (3k), poly[2-benzoyloxy-3-(2,4-dichlorobuenyl)propyl methacrylate] (3m), poly[2-benzoyloxy-3-phenylpropyl methacrylate) (3n)
, poly[2-benzoyloxy-3-(4-methylphenyl)propyl methacrylate-hH3o), poly[2-benzoyloxy-3-(4-methoxyphenyl)propyl methacrylate-N(3p), poly(2-benzoyloxy-3-(4-methoxyphenyl)propyl methacrylate-N(3p) -(4-black,
Lobenzoyloxy)-3-phenylpropyl methacrylate) (3r), poly(2-(4-methoxybenzoyl)-3-phenylpropyl methacrylate) (3g).

The novel polymer of the present invention, Polymer 3a having a benzotriazole group in the side chain, is a useful substance as an adhesive because it has excellent adhesive properties, especially adhesive properties to copper surfaces.

In addition, polymers 3d and 3 have nidroaryl groups in their side chains.
Focusing on the reactivity of the nidroaryl group, f, 3j, 3, and 3 (I) have been found to be crosslinked and insolubilized by light irradiation or electron beam irradiation, so photosensitive resins or radiation-sensitive resists are used. It is a useful substance as

On the other hand, 31 with a chloroaryl group in the side chain of the polymer
, 3o, 3r, etc. are crosslinked and insolubilized by irradiation with electron beams or X-rays, so they are useful as radiation-sensitive resists indispensable in the production of VLSIs and the like.

Furthermore, a polymer having a sulfur element in its side chain, 3h, 3
C, 3a, etc. have excellent radiation resistance due to the sulfur element, and are therefore useful as electric wires and other covering materials and adhesives near the core of nuclear power generation.

In addition, for 3d, 3f, 3jt, 3kt, and 3q, a polymer solution was applied on a glass plate, and after drying, it was confirmed that when irradiated with light for 10 minutes from a distance of 0cm using a 500W ultra-high pressure mercury lamp, it became crosslinked and insolubilized and did not dissolve in ordinary solvents. It was done.

Other functional resins can be easily inferred as natural functions based on the results of previous literature.

The catalyst used in the production of this new polymer has a tertiary amine general formula (R) 3N, a quaternary ammonium salt general formula [(R)
4 N)X and the quaternary phosphonium salt general formula ((R)4
P) X can be used, of which quaternary ammonium salts and quaternary phosphonium salts are preferred (wherein R is an aliphatic group,
(Aromatic groups and alicyclic groups, such as C5 to CtO alkyl groups, phenyl groups, benzyl groups, naphthyl groups, cyclohexyl groups, etc., and X is a halogen or other acid residue)
.

Examples of tertiary amines include triethylamine (TEA),
Tripropylamine (TPA), tri-n-butylamine (TBA), N,N-diethylaniline, N,N-
dimethylaniline, diazabicycloundecene-7, etc., and quaternary ammonium salts include tetramethylammonium bromide (TMAB), tetraethylammonium bromide (TEAB), tetra n-propylammonium bromide (TPAB), and tetra n-butyl. Ammonium bromide (TBAB), tetra n-
Pentylammonium bromide (TP E AB)
, tetra-n-hexylammonium bromide (THA
B), tetra n-octylammonium bromide (T
OAB), tetramethylammonium chloride (T
MAC), tetraethylammonium chloride (T
EAC), tetra n-propylammonium chloride (TPAC), tetra n-butylammonium chloride (TBAC), tetra n-butylammonium iodite, tetra n-butylammonium hydrogen sulfate (TBAH), tetra n-butylammonium verchlorate ( TBAP), tetra n-butylphosphonium bromide (TBPB), benzyltrimethylammonium chromide (BTMAC), cetyltrimethylammonium bromide, penzyltriethylammonium iodide, tetrapropylphosphonium chloride.

These include tetraethylphosphonium iodite, benzyltrimethylphosphonium bromide, and the like.

Solvents used in the addition reaction in the present invention include sulfolane, N-methylpyrrolidone, dimethylformamide, diglyme, dioxane, tetrahydrofuran, cyclohexanone, anisole, toluene, and xylene.

Although not particularly limited, the reaction temperature is about 50 to 200°C, preferably about 90 to 130°C,
Further, the reaction time is usually about 2 to 48 hours.

Examples are shown below. The invention is not limited to these examples.

Glycidyl methacrylate (GMA) (50g:
Using azobisisobutyronitrile (AIBN) (0.5 g) with 0.3 mo I) as a catalyst, toluene (25
0 ml) at 60°C for 5 hours, then in a nitrogen stream for 8 hours.
A radical polymerization reaction was carried out at 0°C for 2 hours to produce PG with a yield of 76%.
Obtained M.A. The polymerization solution was poured into n-hexane, and the resulting polymer was purified by reprecipitation twice with tetrahydrofuran (THE) in n-hexane, filtered, and
It was dried at 0°C. The epoxy equivalent of the obtained polymer was 14
It was 5.7. The reduced viscosity of the polymer in DMF is 0.
It was 24 dl/g (0.5 g/dl concentration, measured at 30°C).

PGMA (1,16 g, 8 mmol) was dissolved in diglyme (20 ml) and 2a (1°9 L)
g, 8 mmol l) and TEAB (0,16 g, o
, 8 mmol 1) was added into the polymer solution. The reaction mixture was stirred at 100° C. for 24 hours and then poured into ethanol. The reaction mixture was reprecipitated twice with tetrahydrofuran (THF) in ethanol at 50°C.
It was vacuum dried.

The yield of polymer was 2.56 g. The addition reaction rate of the polymer was 99.8 mol% (calculated by elemental analysis of N). The reduced viscosity of the polymer in DMF is 0
．． It was 17 dl/g (measured at 30°C and 0.5 g/dl). IR (film): 1720, 1600, 740
,710cm', NMR (CDC13): S=1.0
(C-CH3)yl, 9(C-CH2-C), 4.4 and 4.9(C-CH2-○), 5.7 (0-CH-C
) and 7°2-8.1 (aromatic hydrogen). This is poly[2-benzoyloxy-3-(1-benzotriazolyloxy)propyl methacrylate] (3a).

PGMA (1,16g, 8mmol1) and 2b (2,0
4g, 8mmol 1) in diglyme (20ml)
EAB (0,16gto, 8mm.

l) was reacted at 100°C for 24 hours. Raw
The acid product was purified in the same manner as in Example 1. The final polymer yield was 2.56 g. The addition reaction rate of the polymer was 98.1 mo1% (calculated from elemental analysis of N), and the reduced viscosity of the polymer in DMF was 0.29 dl.
/g (measured at 30°C and a concentration of 0.5 g/dl).

IR (film): 1730, 1670, 1630.1
580.750 and 710 cm-', NMR (CDC1
3): &=1.0(CCH3), 1.9(C-CH2-
C), 3.7 (C-CH2-8).

4.4 (C-CH2-0), 5.9 (0-CH-C)
and 7°O-7,9 (aromatic hydrogen). from this result,
This product is poly[2-benzoyloxy-3-(2-benzoxazolylthiooxy)propyl methacrylate)
(3b).

PGMA (1.16g, 8mmol) was added to diglyme (
TEAB (0.16 g, 0°8 mm) in 20 ml, )
2c (2,17 g
, 8 mmol). The final polymer yield was 2.97 g. The addition reaction rate is 9 from nitrogen analysis.
It was 7.2 mo1%.

The reduced viscosity of the polymer in DMF is 0,16ti
l/g (measured at 30°C and a concentration of 0.5 g/di).

IR (film): 1720, 1600, 750 and 7
10 cm', NMR (CDCl3): E=
1.

0 (C-CH3), 1.9 (C-CH2-C), 3°9
(C-CH2-8), 4.3 (C-CH2-0).

5.7 (C-CH-0) and 7.1-8.0 (aromatic hydrogen). This product is poly[2-benzoyloxy-
3-(2-benzothiazolylthiooxy)propyl methacrylate) (3c).

PGMA (1,16 g, 8 mmol) was dissolved in TEAB (0,16 g, 0°8 mmol) in diglyme (20 ml).
2d (1,95 g
, 8 mmol 1). The final polymer yield was 2.51 g. The addition reaction rate of the polymer is 98
．． It was 5mol1% (result of N analysis). The reduced viscosity of the polymer in DMF was 0.22°d l/g (
(measured at 30°C, 0°5g/dl). IR (film):
1720.1590, 1510, 1340, 750 and 710 cm, NMR (CDC13): g==o,
9 (CCH3), 2.0 (CCH2C), 4°3 (C-
CH2-○), 5.6 (C-CH-○) and 6.8-
8.2 (Aromatic Hydrogen). This polymer is poly(2-
benzoyloxy-3-(4-nitrobuenoxy)propyl methacrylate] (3d).

PGMA (1,16 g) in diglyme (20 ml)
+8 mmol) to 2a (1,71 g, 8 mmol) and TEAB (0,16 g, 0.8 mm.

■) was added. The mixture was stirred at 100° C. for 24 hours. The final polymer yield was 2.23 g. The addition reaction rate was 96.8 mo1% (measured from the intensity ratio of NMR spectra). The reduced viscosity of the polymer in DMF was 0.29 dl/g (30°C, 0.5
g/di).

IR (film): 1720, 750 and 710cm”
', NMR (CDCl3): F==0.9(C
-CH5), 1.9 (C-CH2C), 3.2 (C-
CH2S)-4,3(C-CH20),5゜3(C
-CH-0) and 7.0-8.0 (aromatic protons). This polymer is poly(2-benzoyloxy-3-
thiophenoxypropyl methacrylate) (3e).

PGMA (1.16g, 8mmol) was added to diglyme (
TEAB (0.16 g, O.

gmmol1) for 24 hours at 100°C.
86 g, 8 mmol). The final polymer yield was 2.09 g. The addition reaction rate of the polymer was 74.3mol% (ci analysis and 'H-NMR
(integrated intensity ratio result).

The reduced viscosity of the polymer in DMF was 0.23 dl/g (measured at 30°C and a concentration of 0.5 g/di), IR
(Film): 1720, 1600° 1510 and 71
'Oc m', NMR (CDC13): 1.0
(CCH3), 1.70 (CCH2-c), 4.2 (C
-CH2-0), 5.6 (C-CH-〇) and 6.8
-8.0 (aromatic hydrogen).

This polymer is poly[2-benzoyloxy-3-(4
-chlorophenoxy)propyl methacrylate) (31
).

PGMA (1.16g, 8mmol) was added to diglyme (
TEAB (0.16g, 0°gmm) in 20ml
2q(1,95
g, 8 mmol). The final polymer yield was 1.85 g. The addition reaction rate of the polymer is 9
It was 4.3 mo1% (result of N analysis). The reduced viscosity of the polymer in DMF was 1.02 dl/g (3
(measured at 0°C, 0°5g/dl). IR (film): 1
720.1600, 1530, 1350 and 710cm
”, NMR (CDC13): S=1.0 (CCH3)
, 2.0 (CCH2C), 4.3 (C-CH2-○),
5.6 (C-CH-〇) and 6°90-8.20 (aromatic hydrogen). This polymer is poly(2-(4-nitrobenzoyloxy)3-phenoxypropyl methacrylate) (3q).

1''l In the same manner as in Example 1, PGMA was subjected to an addition reaction with 4-nitrophenyl 4-nitrobenzoate (2f), methylbenzoate (2g), ethylbenzoate (2h) and phenylacetate (21). Each of those polymers is poly(2-(4-nitrobenzoyloxy))
-3-(4-nitrophenyl)propyl methacrylate] (3f), poly[2-benzoyloxy-3-methoxypropyl methacrylate] (3g), poly[2-benzoyloxy-3-ethoxypropyl methacrylate]-
3 (3h) and poly[2-acetoxy-3-phenylpropyl methacrylate] (31).

Similarly, PGMA and 2-nitrophenylbenzoate (2j), 2,4-dinitrobuenylbenzoate (2k), 2,4-dichlorophenylbenzoate (
2m), phenylbenzoate (2n), 4-methyl-
Phenylbenzoate (2o)% 4-methoxyphenylbenzoate (2p), phenyl 4-chlorobenzoate (2r) and phenyl 4-methoxybenzoate (2p)
S) was subjected to an addition reaction. The obtained polymers were poly[2-benzoyloxy-3-(2-nitrophenyl)propyl methacrylate] (3j) and poly[2-benzoyloxy-3-(2゜4-dinitrophenyl)propyl methacrylate] ( 3k), poly(2-benzoyloxy-3-(2,4-dichlorophenyl)propyl methacrylate) (3m), poly(2-
benzoyloxy-3-phenylpropyl methacrylate) (3n), poly[2-benzoyloxy-3-(
4-methylphenyl)propyl methacrylate) (3o
), poly[2-benzoyloxy-3-(4-methoxyphenyl)propyl methacrylate) (3p).

PolyC2-(4-chlorobenzoyloxy)-3-phenylpropyl methacrylate) (3r) and poly(2-
(4-methoxybenzoyl)-3-phenylpropyl methacrylate) (3 g).

The results of the addition reaction are shown in Tables 1 and 2.

Table 1 Addition reaction of PMGA with various active esters a) No.
Ester Time Reaction rate b) Reduced viscosity C) 8 mmo
l h n+ol-% dl/g1 2a
24 99.8 0.172 2a
1095.6 -3 2b 24 98.1
0.294 2b 10 92.8 -
5 2c 24 97.2 0.166
2c 10 95.8 -7 2d
24 98.5 0.228 2e 24
96.8 0.299 2f 4 60.
3 0.2710 2g 24 6.7
-11 2h 10 Trace -
122i 24 28.4 0.20a) Diglyme (
20 ml) at 100°C with 8 mmol of PGMA.

b) Reactivity of epoxy groups in polymer side chains.

c) 0.5 g/dl in DMF, measured at 30°C.

Table 2 Effect of substituents on phenoxyto and benzoate in the addition reaction between PMGA and esters a) No, ester Time Reaction rate b) Reduced viscosity C) 8 mmol
h flol-% d l / g13 2
d 10 78.6 0.2614 2j
10 78.4 0.3615 2k
24 72.6 0.2516 2k 1
0 45.5 -17 21 24 74.3
0.2318 21 10 51.0 0
．． 2519 2m 24 61.5 0.2
320 2n 24 60.0 0.292
1 2n 10 27.7 -
22 2o 24 39.8 -23 2
o 10 24.3 -24 2p
24 28.7 0.3325 2p 10
7.9 -26 2q 24 9
4.3 1.0227 2q 10
80.6 -28 2r 24
67.4 0.2429 2r
10 56.3 -30 2S ・24
44.4 0.2431 2s
10 19.7 -a) b) c) are the same as in Table 1.

The reaction rate between the side chain epoxy group and active ester in the polymer obtained from elemental analysis is in good agreement with the intensity ratio of the NMR spectra of these polymers. This confirms that almost no side reaction between the epoxy group and hydrogen occurred during this reaction.

As seen from Table 1, PGMA and esters 2a, 2
Addition reactions with b, 2C and 2e were performed using TEAB as a catalyst at 100°C, respectively, to form the corresponding polymers 3a.
, 3b, 3c and 3e can be selectively produced. Also, 4-
Reaction with nitrophenyl 4-nitropenzoate (2f) gives the corresponding polymer 3f at 100 DEG C. for 4 hours with a conversion of 60.3 mol %. In addition, methyl benzoate (2g), phenylacetate-(2i) was heated at 100°C.
, 3 g and 31 of the corresponding polymers were obtained in yields of 6.7 mol % and 28.4 mol %, respectively, in 24 h.
Reaction with ethyl benzoate (2h) at 100°C, 10
It didn't happen much even in time.

From this result, in the reaction of this side chain epoxy group-containing polymer and active ester in the presence of a catalyst such as TEAB, the reaction with an ester having an electron-withdrawing group on phenoxy or benzoate results in a relatively high yield. Although polymers are obtained, the reaction of esters with electron-donating groups on phenoxy or benzoate shows that the corresponding polymers cannot be obtained in high yields under the same conditions.

Large Breath Main PGMA (1.16g, 8mmol) 2d and 2
e (1,95gt 8mmol) each.

Various catalysts (0,8 mmo
The reaction was carried out at 100° C. for 10 hours in the presence of 1).

The results are shown in Tables 3 and 4.

Table 3 PMGA and 4-nitrophenylbenzoate No.
Catalyst Reaction rate b) Reduced viscosity C) 32 TM
AB 47.2 0.2413 TEAB
78.6 -0.2633 TPAB
82.5 0.2634 TBAB 8
2.6 0.2535 TPEAB78.6
0.2436 THAB 66.2
0.2337 TOAB 20.5 0.
2338 TMAC62,90,22 39TEAC74,10,23 40TPAC70,40,24 41TBAC67,90,22 42TBAI 80.3 0.2643
TBAH4,00,68 44TBAP Trace O,254
5TBPB 80.9 0.2846
BTMAC69,00,2347TEA
59.1 0.4748 TBA
33.3-a) React with 8 mmol of PGMA in diglyme (20 ml) at 100° C. for 10 hours using 0.8 mmol of catalyst.

b) Reactivity of epoxy groups in polymer side chains.

c) Measured in DMF at 0.5 g/di at 30°C.

Table 4 PMGA and phenylthiobenzoate (2e) No.
Catalyst Reaction rate b) Reduced viscosity C) 50 T
EAB 60.2 0.2951 TPA
B 78.2 0.2152 TBAB
81.8 0.2053 TPEAB7
3.1 0.2254 THAB
61.9 0.2255 TOAB
4.8 0.2256 TMA
C80,80,2457TEAC86,20,20 58TPAC83,80,21 59TBAC82,30,21 60TBAI 33.3 0.24$1
TBAHTrace-62TBAP
Trace-63TBPB
44.2 0.2864TEA
9.2 -65 TBA Tr
ace - As can be seen from Table 3, in the catalyst, when the active ester is 4-nitrophenylbenzoate (2d), the quaternary ammonium salt has high catalytic activity when the counter anion is B r-1C1- and Ni. obtained, H8O: or CIO♂ does not show very high catalytic activity, and the catalytic activity is very strongly influenced by the alkyl chains in the quaternary salts, with TPAB (propyl) and TBAB (butyl) ) has the highest activity in the series of quaternary ammonium salts containing Br″″ anions.

On the other hand, in the series of CI-anion-containing quaternary ammonium salts, TEAC showed higher activity than other catalysts. It is believed that the activity of a catalyst in the reaction between a side chain epoxy group in a polymer and an active ester is determined by the lipophilic relationship between the reagents, the steric hindrance of the catalyst, and the weakness of the counter anion of the catalyst. As a catalyst in this reaction, the specific quaternary ammonium salt has higher activity than tertiary amines such as TEA and TBA.

Also, as seen from Table 4, when the ester is phenylthiobenzoate (2B), Br-
Among the series of quaternary ammonium salts containing , TBAB has the highest activity, and TMAB shows almost no activity.

On the other hand, in the case of C1-containing ammonium salt series, TEA
C shows the highest activity. TBAI, TBPB and TEA
In this reaction system, the activity is significantly reduced. and T.B.A.
H, TBAP and TBA had no activity.

Furthermore, certain quaternary salts with a C1-anion have higher activity in the reaction of thioester compound (2e) than quaternary salts with a Br-anion.

Furthermore, it can be concluded that certain active esters have a higher reactivity towards epoxy groups in polymers than carboxylic acids. In each reaction, it is important to select a suitable catalyst system.

A benzotriazole in the side chain, which is an addition reaction product of the side chain epoxy group-containing polymer of the present invention and a benzoate containing a benzotriazole group, a nidroaryl group, a chloroaryl group, or a sulfur element in the molecule. Resins with functionalities such as nitroaryl groups, nidroaryl groups, and chloroaryl groups are new polymers, and can be used as resins with excellent adhesiveness, photosensitivity, radiation sensitivity, or radiation resistance, and are extremely useful resins. I can say that.

Claims (1)

[Claims] A functional polymer having a repeating structure represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, n is 10 to 10,000, X is O or S, and R_1 is a nitro group or a halogen group. R_2 is an alkyl group, an aryl group, an aralkyl group, a nitro group or a halogen-substituted aryl group, a benzotriazole group, a benzoxazole group, or a benzothiazole group.