JPS61227844A - Catalyst for addition reaction of polymer containing side-chain epoxy group and activated ester - Google Patents

Abstract

PURPOSE:To perform the additional reaction of side-chain epoxy group and activated ester in the high rate of reaction by using a compd. selected from among tertiary amine, quaternary ammonium salt and quaternary phosphonium salt as a catalyst. CONSTITUTION:The additional reaction of both the various polymers contg. side-chain epoxy group such as glycidyl acrylate and activated esters especially benzoate having an electron attractive substituent group is performed by using one or more kinds of compds. selected from among tertiary amine (R)3N, quater nary ammonium salt [(R)4N]X and quaternary phosphonium salt [(R)4P]X (in a formula, R is an aliphatic group, an aromatic group and an alicyclic group and X is halogen or the other acidic group). Thus the functional high molecule is produced in the excellent rate of reaction but especially quaternary salt is excellent as the catalyst and the obtained polymer is available in the various applications such as an adhesive and a photoresist.

Description

[Detailed description of the invention] Hiko] Shihi Qo Dan Rita! □ The present invention combines side chain (pendant) epoxy □ groups in polymers with active esters, particularly poly(glycidyl methacrylate).
The present invention relates to useful catalysts for the production of functional polymers by the reaction of benzoates containing electron-withdrawing groups.

Techniques to Solve Problems Poly(glycidyl methacrylate) and its copolymers are attracting attention as reactive (functional) polymers. and,
Addition reactions between poly(glycidyl methacrylate-1) or other polymers containing epoxy groups in their side chains and amines, alcohols, phenols, and carboxylic acids have been reported [Iwakura and Kurita, co-authored ""ReactivePolymer" Kodansha (
(1977), Polymer Chemistry J Vol. 25, p. 412 (1)
968), J., Pol ym, Sci., Pal.
ym, Symp, No, 47. p155 (1974
), Makromol, Chem, 36y p199
(1974), Makromol, Chem, 183.
p203 (1982)).

This side chain epoxy group-containing polymer is widely used as a raw material for the synthesis of functional polymers and crosslinkable polymers.
) reported that a photosensitive polymer was obtained by addition-reacting the side chain epoxy group in a copolymer and a photoreactive carboxylic acid using a quaternary ammonium salt as a catalyst [Kobunshi Papers. Vol. 32, p. 604 (1975)). However, the polymers obtained in these reactions have β-hydroxy groups in their side chains, and the hydroxy groups in the resulting polymers have problems in terms of electrical properties, lipophilicity, and stability.

1-jellman et al. used BF as a catalyst.
3.('CH) 20 was used to form a polymer with azlactone side chain and 2-hydroxylethyl methacrylate-1.
・It has been reported that a new photosensitive polymer with a side chain hydroxyl group was obtained by an addition reaction (J,
Polym, Sci, IPolym, Chem, E
d, -22, pH 79 (1984)).

In addition, recently, the present inventors have combined the side chain epoxy U in the GMA domethyl methacrylate copolymer with cinnamoyl chloride, 4-nitrophenyl cinnamate, etc. by tertiary amine,
reported that they succeeded in conducting an addition reaction using a quaternary salt as a catalyst, and these tertiary amines and quaternary salts
proposed that class salts are useful as catalysts in the addition reaction [J, Po lym, Sci,, Po
lym, Cbem, Ed,,2]-,p229]
(1983), Polymer J, r±6,37
1 (1984), JP-A-59-2161.38].

, In order to solve one problem -o-tm As a result of further investigation of addition reactions with polymers containing epoxy groups in the side chains, the present inventors found that tertiary amines, quaternary ammonium salts and quaternary phosphonium salts A catalyst consisting of one or more selected from the following has an excellent effect on addition reactions between polymers having epoxy groups in their side chains and esters other than cinnamate esters, and produces novel and useful polymers in high yields. The present invention was achieved by discovering what could be done.

That is, the present invention provides a method for addition reaction between a pendant epoxy group in a polymer and an active ester, which is characterized by comprising a tertiary amine, a quaternary ammonium salt, and a quaternary phosphonium salt. Regarding catalysts, 1-.

In the present invention, the tertiary amine which is the catalyst used in the addition reaction has the general formula (R,)3N, the quaternary ammonium salt has the general formula 1:(R)4N]x and the quaternary phosphonium salt has the general formula [(R)4p), x (wherein R is an aliphatic group, aromatic group, or alicyclic group, and 01 to
C2o alkyl group, phenyl group, benzyl group, naphthyl group, cyclohexyl group, etc., and X is halogen or other acid residue).

Examples of tertiary amines include triethylamine (TEA),
1-lipropylamine (TPA), ) n-butylamine (TBA), N,N-diethylaniline, N,N
-dimethylaniline, diazabicycloundecene-7, etc. Quaternary ammonium salts include tetramethylammonium bromide (TMAB), tetraethylammonium chloride (TEAB), tetra n-propylammonium bromide (TPAB), tetra n- Butylammonium bromide (TBAB), tetra n-
Pentylammonium bromide (TPEAB), tetra n-hexylammonium bromide (THAB),
Tetra n-octylammonium bromide (TOAB
), tetramethylammonium chloride (TMAC)
, tetraethylammonium chloride (TEAC)
, tetra n-propylammonium chloride (TP
AC), tetra n-butylammonium chloride (T
BAC), tetra n-butylammonium goudide,
Tetra n-butylammonium hydrogen sulfate (TBAH, ), tetra n-butylammonium perchlorate (TBAP), tetra n-butylphosphonium bromide (TBPB, ), benzyltrimethylammonium chromide (BTMAC), cetyltrimethylammonium bromide, penzyl These include triethylammonium iodide, tetrapropylphosphonium chloride, tetraethylphosphonium iodite, benzyltrimethylphosphonium, and nium bromide.

The novel addition reaction of the present invention is as shown by the following general formula.

As the side chain epoxy group-containing polymer, for example, a homopolymer or copolymer of glycidyl acrylate, allyl glycidyl ether, p-vinylphenyl glycidyl ether, etc. is used. 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. .

Examples of esters that undergo an addition reaction with the side chain epoxy group-containing polymer include the following.

1-penzotriazoylyl benzoate (2a), 2-
Benzoxazolylthiobenzonyh (2b), 2-benzothiazolylbenzoate (2c), 4-nitrophenylbenzoate (2d), phenylthiobenzonyh
(2e), 4-nitrophenyl-4-di-lobenzoate (2f), methylbenzoate (2g), ethylbenzoate (2h), phenylacetate-h(2+), 2
-nitrophenylbenzoate (2j), 2,4-dinitrophenylbenzony-'/-to (2k), 4-chlorophenylbenzoate (21)
, 2,4-dichlorophenylbenzoate (2m), phenylbenzonyh (2n), 4-methylphenylbenzoate (20), 4-methoxyphenylbenzoate (2p), phenyl 4-nitropenzoate (2q),
Phenyl 4-chlorobenzoate (2r) and phenyl 4-methoxybenzoate (2s), 4-benzoylphenylbenzoate (2t), phenyl 4-benzoylbenzoate (2u), 2.4 + 6-dolinitrophenylbenzoate (2v) , phenyl 2,4.6
-dolinitrobenzoate (2w), 2,4-dibromphenylbenzoate (2x), 4-iodophenylbenzoate (2y), 4-acetylphenylbenzoate (2z), and the like. Also, two of these esters
Benzoates having electron-withdrawing substituents other than g, 2h, 2i, 2n, 2p, and 2s are active esters useful in the reactions of the present invention.

These benzoates can be produced by the reaction of the corresponding benzoyl chlorides and phenols, and some can be produced by the reaction of benzoates and phenols in the coexistence of 8O3H).

The novel polymers obtained by the present invention are, for example, poly[2-benzoyloxy-3-(1-benzotriazolyloxy)propyl methacrylate) (3a), poly[2-benzoyloxy-3-(2-penzoyloxy) Zolylylthiooxy)propyl methacrylate] (3b)
, poly[2-benzoyloxy-3-(2-benzothiazolylthiooxy)propyl methacrylate] (3c)
, poly[2-benzoyloxy-3-(4-nitrophenoxy)propyl methacrylate) (3d), poly[2
-benzoyloxy-3-thiophenoxypropyl methacrylate] (3e), poly(2-benzoyloxy-
3-(4-chlorophenoxy)propyl methacrylate) (3f), poly(2-(4-nitrobenzoyloxy)~3-phenoxypropyl methacrylate) (3g)
etc.

As the solvent used in the addition reaction in the present invention, common solvents such as sulfolane, N-methylpyrrolidone, dimethylformamide, diglyme, dioxane, tetrahydrofuran, cyclohexanone, anisole, toluene, and xylene can be used. Hydrogen-containing alcohols, phenols, and carboxylic acids are unsuitable as solvents for this reaction.

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.

In addition, as the reactive polymer having an epoxy group in the side chain used in the present invention, polyglycidyl methacrylate (PGMA), which is a polymer of glycidyl methacrylate (GMA), which is a typical reactive monomer, was used. Copolymers of GMA and other monomers, glycidyl acrylate polymers or copolymers of this monomer and other monomers, allyl glycidyl ether polymers, and copolymers of GMA and other monomers. This addition reaction can also be applied to reactions with many polymers having epoxy groups, such as copolymers of -, epoxidized polybutadiene, and epoxidized polyisoprene.

Examples are shown below. It goes without saying that the present invention is not limited to these examples.

PGMA (1,16 g + gmmol) was dissolved in diglyme (20 ml) and then 2a (1°91
g, gmmol) and TEAB (0,] 6g
+ o, gmmo ]) 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 recrystallized twice from tetrahydrofuran (THF) in ethanol and
Vacuum drying was performed at 50°C.

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). Its poly-1 in DMF
The reduced viscosity of 1=mer was O, 1.7 dl/g (at 30°C
, 0.5 g/dl). TR (film): 1
,720,1,600,740,710cm', NMR
(CDCl2): g=1.0(C-CH3).

1.9 (C-CH2-C), 4.4 and 4.9 (C-C
I-T2-0), 5.7 (0-CH-C) and 7゜2
-8.1 (aromatic hydrogen). This one is poly[2-
benzoyloxy-3-(1-benzotriazolyloxy)propyl methacrylate) (3a).

PGMA (1.16g, 8rnmol) and 2b<2.
04 g + gmmol) and diglyme (20ml
) Medium TEAB (0.16g, 0.8mm.

l) was reacted at 100°C for 24 hours. The product was purified as in Example 1. The final polymer yield is 2.
It was 56g. The addition reaction rate of the polymer is 98.1
The mo amount was 1% (calculated from elemental analysis of N). The reduced viscosity of the polymer in DMF was 0.29 dl/g (30°C, 0.5 g/d
(measured at a concentration of 1).

IR (film): 1730, 1670, 1630.1
580.750 and 710 cm-', NMR (CDCl
3): Dan=l, 0(C-CH3), 1.9(c
CH2-C), 3.7 (CCH2S).

4.4 (C-CH2-0), 5.9 (0-(j(-C
) and 7.0-7.9 (aromatic hydrogen). From this result, this product is poly[2-benzoyloxy-3-(2
-benzoxazolylthiooxy)propyl methacrylate) (3b).

PGMA (1,16 g, gmmo 1) in diglyme (20 ml) T E A B (0-16 g p
O.

gmmol) at 100°C for 24 hours at 2C (2
, 17gt gmmol). The final polymer yield was 2.97 g. The addition reaction rate was 97.2 mo1% based on nitrogen analysis.

The reduced viscosity of the polymer in DMF is 0.16 d]/
g (measured at 30° C. and a concentration of 0.5 g/dl).

TR ('film): 1720, 1600, 75
0 and 710 cm-■, NMR (CDCI3): E=1
°0 (C-CH3), 1.9 (C-CH2-C), 3°9 (C-C112-8), 4.3 (C-CH2-0).

5, 7 (C-CH-○) and 7.1-8.0 (aromatic hydrogen). This product is poly[2-benzoyloxy-
3-(2-benzothiazolylthiooxy)propyl methacrylate) (3c).

PGMA (1,16g*8mmol) was dissolved in TEAB (0,'16g,'0°8) in diglyme (20ml).
2d(1,
95 g, 8 mmol). The final polymer yield was 2.51 g. The addition reaction rate of the polymer was 98.5 mo1% (result of N analysis). The reduced viscosity of the polymer in DMF was 0.22 dl/g (
Measured at 30'C10°5g/di). IR (film)
: ] 720.1590, 1510, 1340.750 and 710 cm-', NMR (CDCI3): g = 0.9
(C-CH3), 2.0 (CC82G), 4°3 (C-
CH2-○), 5.6 (C-CH-0) and 6.8
-8.2 (aromatic hydrogen). This polymer is poly[2
-benzoyloxy-3-(4-nitrophenoxy)propyl methacrylate] (3d).

PGMA (1,16 g) in diglyme (20 ml)
, 8 mmol) to 2 g (1,71 g + 8 mmol
) and TEAB (0.16g, 0.8mm.

l) 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 the NMR spectrum). The reduced viscosity of the polymer in DMF was 0.29 dl/g (30°C, 0.5 g/g).
dl concentration (measured at a constant value of 15).

TR (film): 1720, 750 and 710 cm-
1, NMR (CDCI3): g=o, 9(C-C
Summer (3)-1, 9 (CC82C), 3. 2
(C-CH2-8), 4.3 (C-CH2-0), 5
°3 (C-CH-0) and 7.0-8.0 (aromatic protons). This polymer is poly(2-benzoyloxy-3-thiophenoxypropyl methacrylate-h) (3
e).

PGMA (1,16 g, 8 mm I) in diglyme (20 ml) with TEAB (0,16 g, 0°3 mm
21 (1,86 g
, 8 mmol). The final polymer yield was 2.09 g. The addition reaction rate of the polymer is 74
．． 3 mo1% (results of C1 analysis and integrated intensity ratio of 'H-NMR).

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° 15IO and 71
0 cm', NMR (CDCI 3): 1.0 (C
-CH3), 1.70(C-CH2-C), 4.2(C
-CH2-0), 5.6 (C-CH-○) and 6.
8-8.0 (aromatic hydrogen).

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

PGMA (1,16 g, 8 mmol) was dissolved in TEAB (0,16 g, 0°8 mmol) in diglyme (20 ml).
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
-1, NMIR(CDCl3): i=1, O
(CCH3), 2.0(C-CH2-C), 4.3(C
-CH2-0), 5.6 (C-CH-0) and 6゜9
0-8.20 (aromatic hydrogen). This polymer is poly(2-(4-nitrobenzoyloxy)3-phenoxypropyl methacrylate) (3q).

In dog 11, PGMA was subjected to an addition reaction with 4-21-lophenyl 4-nitrobenzoate (2f), ethylbenzoate (2h), and phenylacetate (21) in the same manner as in Example 1 above. Each of those polymers is poly(2-(4-
Nitrobenzoyloxy)-3-(4-21-buenyl)propyl methacrylate) (3f), Poly[2-benzoyloxy-3-methoxypropyl methacrylate] (3g), Poly[2-benzoyloxy-3-propyl methacrylate] l~
xypropyl methacrylate) (3h) and poly[2-
Acetoxy-3-phenylpropyl methacrylate] (
3i).

Similarly, PGMA and 2-nitrophenylbenzoate (2j), 2.4-dinitrophenylbenzoate (2k), and 2.4-dichlorophenylbenzoate (
2m), phenylbenzoate (2n), 4-methyl-
Phenylbenzony]-(2o), 4-methoxyphenylbenzoate (2p), phenyl 4-chlorobenzoate (2r) and phenyl 4-methoxybenzoate (2S) were 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) (3mm, poly(2-benzoyloxy-3-(2,4-dichlorophenyl)propyl methacrylate) 3-phenylpropyl methacrylate) (3n
), poly[2-benzoyloxy-3-(4-methylphenyl)propyl methacrylate] (3o), poly[2-benzoyloxy-3-(4-methoxyphenyl)propyl methacrylate) (3p), poly(2- (4
-chlorobenzoyloxy)-3-phenylpropyl methacrylate) (3r) and poly(2-(4-methoxybenzoyl)-3-phenylpropyl methacrylate)
(38) etc.

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

Table 1 No, ester time reaction rate b) reduced viscosity C
)1 2a 24 99.8. 0.172
2a 10 95.6 -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 0.27=20- 10 2g 24 6.7 -11
2h 10 Trace
-122+ 24 28.4 0.
208) Using TEAB as a catalyst, 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
mol-% dl/g13 2d 10
7B, 6 0.2614 2j 1078
．． 4 0.3615 2k 24 72.6
0.2516 2k 10 45.5
-17 21 24 74.3 0.231B
21 10 51.0 0.2519
2m 24 61.5 0.23
20 2n 24 60.0
0.292+ 2n 10 27
．． 7 -22 '2o 24
39.8 -23 2o 10
24.3 -24 2p 24
28.7 0.3325 2p 1
0 7.9 -26 2q 24
94.3 1.0227 2q
10 80.6 -28 2r
24 67.4 0.2429 2r
1,0 56.3 -30 2
s 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, with 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 (2 g) and phenylacetate (2I) were heated at 100°C.
In 24 hours, 3 g of the corresponding polymer and 6
．． Although the yields were 7 mol% and 28.4 mol%, almost no reaction with ethyl benzoate (2h) occurred even at 100°C for 10 hours.

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.

・ 2d and 2d of JJ degree PGMA (], 16g, 8mmol)
e (1.95 g + 8 mmol) in diglyme (20 ml) in the presence of various catalysts (0.8 mmol) at 100° C. for 10 hours.

The results are shown in Tables 3 and 4.

Table 3 PMGA and 4-nitrophenylbenzoate N o ,
Catalyst Reaction rate b) Reduced viscosity C) 0.8 m
mol mol-% dl/g32
TMAB 47.2 0.2413 T
EAB 78.6 0.2633 TPA
B 82.5 0.2634 TBAB
82.6 0.2535 TPEAB78
．． 6 0.2436 THAB 66.2
0.2.337 TOAB '20.5
0.2338' TMAC62,90,
2239TEAC74,10,23 40TPAC70,40,24 41TBAC67,90,22 42TBAI 80.3 0.2643
TBAH4,00,68 44TBAP Trace O,254
'5 TBPB 80L 9
0. 2846 BTMAC69,OO,234
7TEA 59.1 0.4748
TBA 33.3 -a) in diglyme (20 ml) with 0.8 mmol of catalyst,
React with 8 mmol of PGMA at 100°C for 10 hours.

b) Reactivity of epoxy groups in polymer side chains.

c) 0.5 g/dl in DMF, measured at 30°C.

Table 4 Catalytic effect in the addition reaction between PMOA and phenylthiobenzoate (2e) a) No, catalyst reaction rate b) Reduced viscosity C)
0.8 mmol mol-% d l /
g49 TMAB Trace O,245
0TEAR60,20,29 51TPAB 78.2 0.2152
TBAB 81.8 0.2053 TP
EAB73.1 0.2254 TBAl3
61.9 0.2255 TOAB
4.8 0.2256 TMAC80,80,
24 57TEAC86,20,20 58TPAC83,80,21 59TBAC82,30,21 60TBAT 33.3 0.2461
TBAHTrace -62TBAP Trac
e-63TBPB 41.2 0°2864
TEA 9.2 -65
TBA Trace-a)b)c
) is the same as Table 3.

As can be seen from Table 3, in the catalyst, when the active ester is 4-nitrophenylbenzoate (2d), high catalytic activity is obtained when the counter anion is Br-2CI- and I- in the quaternary ammonium salt. H3O4- or ClO3- does not show very high catalytic activity. And the catalytic activity is very strongly influenced by the alkyl chain in the quaternary salt, where TPAB (propyl) and TB
It is shown that AB (butyl) has the highest activity in the series of quaternary ammonium salts containing Br-anions.

On the other hand, in the series of quaternary ammonium salts containing C1-anions, 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 (2e), 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 1, C1-containing ammonium salt series, TE
AC shows the highest activity. TBAl, TBPB and TE
The activity of A is significantly reduced in this reaction system. And T.B.
AT-1, TBAP and TBA had no activity.

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

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.

The present invention provides a catalyst for a novel addition reaction between a pendant epoxy group in a polymer and an active ester, one selected from tertiary amines, quaternary ammonium salts, and quaternary phosphonium salts. By using the catalysts described above, useful functional polymers can be produced with excellent reaction rates, and particularly remarkable effects can be obtained with quaternary salts. New polymers can be used in adhesives,
It is useful as a coating material, a photoresist, an electron beam sensitive resist, a radiation resistant material, etc., and can be said to be an excellent invention.

Claims (3)

[Claims] (1) A catalyst for the addition reaction between a pendant epoxy group in a polymer and an active ester, characterized by comprising one or more of a tertiary amine, a quaternary ammonium salt, and a quaternary phosphonium salt. (2) The addition reaction catalyst according to claim 1, wherein the active ester is an ester having an electron-withdrawing group on phenoxy or benzoate. (3) The addition reaction catalyst according to claim 1 or 2, wherein the quaternary ammonium salt contains Br, Cl, or I anion.