JPH0422162B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to functional polymers, particularly novel adhesive, photosensitive, radiation sensitive and radiation resistant polymers. PRIOR ART AND PROBLEMS TO BE SOLVED Polymers containing side chain epoxy groups are widely used as raw materials for the synthesis of functional and crosslinkable polymers, and the present inventors have developed glycidyl methacrylate (GMA). The side chain epoxy group in the copolymer and the photoreactive carboxylic acid are subjected to an addition reaction using a quaternary ammonium salt as a catalyst to obtain a photosensitive polymer [Kobunshi Ronshu Vol. 32, p. 604 ( 1975)], and recently, the present inventors have combined the side chain epoxy group in GMA and methyl methacrylate copolymer with 4-nitrophenyl cinnamate using a tertiary amine or quaternary ammonium salt as a catalyst. proposed that an addition reaction be carried out 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 cinnamate esters in the side chains, they have no effect on other properties such as adhesion, sensitivity, radiation sensitivity, and radiation resistance. . Means for Solving the Problems As a result of further investigation of the addition reaction products of esters and polymers containing pendant epoxy groups, the present inventors found that esters containing benzotriazole, thiobenzothiazole, and thiobenzoxazole groups The selection of benzoates, unlike the reaction products with cinnamic acid and cinnamate esters, improves adhesion, photosensitivity due to nitro and chloro groups, radiation sensitivity or resistance due to elemental sulfur. The present invention was achieved by discovering that it is possible to produce a new radioactive polymer. That is, the present invention provides a functional polymer having a repeating structure represented by the following general formula. 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. In R ₂ above, the alkyl group is methyl, ethyl group, isobutyl group, tert-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-trinitrophenyl, 2,4-dinitronaphthyl, 4-nitronaphthyl, 2-nitronaphthyl groups, etc., and halogen group substitutions include 4-chlorophenyl, 2,4-dichlorophenyl, 2,
4,6-trichlorophenyl, 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. (In the formula, n is 10 to 10,000, preferably 100 to 10,000
and X, R ₁ and R ₂ 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, and p-vinylphenyl glycidyl ether. used. In the case of copolymers, methyl acrylate, ethyl acrylate, butyl methacrylate, styrene,
Vinyl acetate, N-vinylpyrrolidone, etc. are copolymerized and used in a proportion of about 80 mol % or less, preferably about 55 mol % or less. Polymers containing side chain epoxy groups in the present invention, such as polyglycidyl methacrylate (PGMA)
The viscosity (or molecular weight) of glycidyl methacrylate (GMA) can be easily adjusted by changing the initiator concentration, monomer concentration, polymerization temperature, etc. during radical polymerization of glycidyl methacrylate (GMA), and from a practical standpoint, n=
It has a degree of polymerization of 10 to 10,000, preferably 10 to 10,000. Substituted benzoates include 1-benzotriazoylyl benzoate (2a), 2-benzoxazoylthiobenzoate (2b), 2-benzothiazolylthiobenzoate (2c), 4-nitrophenylbenzoate (2d), ruthiobenzoate (2e), 4-nitrophenyl-4-nitrobenzoate (2f), 2-nitrophenylbenzoate (2j), 2,4-dinitrophenylbenzoate (2k), 4-chlorophenylbenzoate (2l), 2 , 4-dichlorophenylbenzoate (2o), phenyl 4-nitrobenzoate (2q),
Phenyl 4-chlorobenzoate (2r) has a benzotriazole group, nitroaryl group, etc. in the molecule,
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 polymer obtained by the present invention is, for example, poly[2-benzoyloxy-3-
(1-Benzotriazolyloxy)propyl methacrylate] (3a), poly[2-benzoyloxy-3-(2-benzoxazolylthiooxy)
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] (3l), poly[2- (4-nitrobenzoyloxy)-3-phenoxypropyl methacrylate] (3q), poly[2-(4-nitrobenzoyloxy)-3-(4-nitrophenyl)propyl methacrylate] (3f), poly[2-
Benzoyloxy-3-methoxypropyl methacrylate] (3g), poly[2-benzoyloxy-3-ethoxypropyl methacrylate] (3h),
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-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), poly[2-(4-chlorobenzoyloxy)-3-phenylpropyl methacrylate]
(3r), poly[2-(4-methoxybenzoyl)-3
-phenylpropyl methacrylate] (3s). 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. Polymers with nitroaryl groups in their side chains
Focusing on the reactivity of the nitroaryl group, 3d, 3f, 3j, 3k, and 3q have been found to be crosslinked and insolubilized by light irradiation or electron beam irradiation. It is a substance useful as On the other hand, 3l, 3o, 3r, etc., which have a chloroaryl group in the side chain of the polymer, are crosslinked and insolubilized by irradiation with electron beams or X-rays, so they are useful as radiation-sensitive resists that are indispensable in the production of ultra-LSI devices. Furthermore, a polymer having a sulfur element in its side chain,
3h, 3c, 3e, etc. have excellent radiation resistance due to the sulfur element, so they are useful as electrical wires and other covering materials and adhesives near the core of nuclear power plants. In addition, for 3d, 3f, 3j, 3k, and 3q, each polymer solution was applied on a glass plate, and after drying, it was irradiated with light from a 10 cm distance from a 500 W ultra-high pressure mercury lamp for 10 minutes, resulting in crosslinking and insolubilization, and it was found that it did not dissolve in ordinary solvents. confirmed. Other functional resins can be easily inferred as natural functions based on the results of previous literature. The catalysts used in the production of this new polymer include a tertiary amine general formula (R) ₃ N, a quaternary ammonium salt general formula [(R) ₄ N]X, and a 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, an aromatic group, an alicyclic group, a C ₁ to _{C 10} alkyl group, a phenyl group , benzyl group, naphthyl group, cyclohexyl group, etc., and X is a halogen or other acid residue). Examples of tertiary amines are triethylamine (TEA), tripropylamine (TPA), trin
-butylamine (TBA), N,N-diethylaniline, N,N-dimethylaniline, diazabicycloundecene-7, etc. Quaternary ammonium salts include tetramethylammonium bromide (TMAB), tetraethylammonium bromide ( TEAB), tetra n-propylammonium bromide (TPAB), tetra n-butylammonium bromide (TBAB), tetra n-pentylammonium bromide (TPEA), tetra n
-hexylammonium bromide (THAB),
Tetra n-octylammonium bromide (TOAB), tetramethylammonium chloride (TMAC), tetraethylammonium chloride (TEAC), tetra n-propylammonium chloride (TPAC), tetra n-butylammonium chloride (TBAC), tetra n-butylammonium Iodide, tetra n-butylammonium hydrogen sulfate (TBAH), tetra n-butylammonium perchlorate (TBAP), tetra n-butylphosphonium bromide (TBPB), benzyltrimethylammonium chromide (BTMAC), cetyltrimethylammonium bromide, These include benzyltriethylammonium iodide, tetrapropylphosphonium chloride, tetraethylphosphonium iodide, 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, and the reaction time is usually about 2 to 48 hours. Examples Examples are shown below. The invention is not limited to these examples. Synthesis of poly(glycidyl methacrylate) (PGMA) Glycidyl methacrylate (GMA) (50g:
Using azobisisobutyronitrile (AIBN) (0.5 g) with 0.3 mol) as a catalyst, toluene (250
ml) at 60°C for 5 hours, then 80°C in a nitrogen stream.
The radical polymerization reaction was carried out at ℃ for 2 hours, with a yield of 76%.
Got PGMA. The polymerization solution was poured into n-hexane, and the resulting polymer was then purified by reprecipitation twice with tetrahydrofuran (THF) in n-hexane, filtered, and dried at 50°C under reduced pressure. The epoxy equivalent weight of the obtained polymer was 145.7. The reduced viscosity of the polymer in DMF was 0.24 dl/g (0.5 g/dl concentration, measured at 30°C). Example 1 Production of poly[-2benzoyloxy-3-(1-benzotriazolyloxy)propyl methacrylate] (3a) PGMA (1.16 g, 8 mmol) was mixed with diglyme (20
ml) and then 2a (1.91 g, 8 mmol)
and TEAB (0.16 g, 8 mmol) were added into the polymer solution. The reaction mixture was heated to 100 °C for 24
Stir for an hour and then pour into ethanol.
The reaction mixture was reprecipitated twice with tetrahydrofuran (THF) in ethanol and dried under vacuum 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). The reduced viscosity of the polymer in DMF was 0.17 dl/g (30°C, 0.5
(measured in g/dl). IR (Film): 1720, 1600,
740, 710 cm ^-1 , NMR (CDCl ₃ ): δ = 1.0 (C-
CH ₃ ), 1.9 (C-CH ₂ -C), 4.4 and 4.9 (C-CH ₂
-O), 5.7 (O-CH-C) and 7.2-8.1 (aromatic hydrogen). This is poly[2-benzoyloxy-3-(1-benzotriazolyloxy)propyl methacrylate] (3a). Example 2 Production of poly[2-benzoyloxy-3-(2-benzoxazolylthiooxy)propyl methacrylate] (3b) PGMA (1.16 g, 8 mmol) and 2b (2.04 g, 8 m
mol) and TEAB (0.16 g,
8 mmol) at 100°C for 24 hours.
The product was purified as in Example 1. The final polymer yield was 2.56 g. The addition reaction rate of the polymer was 98.1 mol% (calculated from elemental analysis of N). The reduced viscosity of the polymer in DMF is 0.29
dl/g (measured at 30°C and a concentration of 0.5 g/dl). IR (Film): 1730, 1670, 1630, 1550, 780
and 710 cm ^-1 , NMR (CDCl ₃ ): δ = 1.0 (C-
CH ₃ ), 1.9 (C-CH ₂ -C), 3.7 (C-CH ₂ -S),
4.4 (C- _CH2 -O), 5.9 (O-CH-C) and 7.0-
7.9 (aromatic hydrogen). From this result, this product is poly[2-benzoyloxy-3-(2-benzoxazolylthiooxy)propyl methacrylate] (3b). Example 3 Production of poly[2-benzoyloxy-3-(2-benzothiazolylthiooxy)propyl methacrylate] (3c) PGMA (1.16 g, 8 mmol) was mixed with diglyme (20
ml) in the presence of TEAB (0.16 g, 0.8 mmol),
It was reacted with 2c (2.17 g, 8 mmol) at 100° C. for 24 hours. The final polymer yield was 2.97g. The addition reaction rate was 97.2 mol% based on nitrogen analysis.
The reduced viscosity of the polymer in DMF is 0.16 dl/
g (measured at 30°C and a concentration of 0.5 g/dl). IR (Film): 1720, 1600, 750 and 710cm ^- ₁ ,
NMR (CDCl ₃ ): δ = 1.0 (C-CH ₃ ), 1.9 (C-
_CH2 -C), 3.9(C-CH2 _- S), 4.3(C- _CH2-
O), 5.7 (C-CH-O) and 7.1-8.0 (aromatic hydrogen). This product is poly[2-benzoyloxy-
3-(2-benzothiazolylthiooxy)propyl methacrylate] (3c). Example 4 Poly[2-benzoyloxy-3-(4-nitrophenoxy)propyl methacrylate]
Production of (3d) PGMA (1.16 g, 8 mmol) was added to diglyme (20
ml) in the presence of TEAB (0.16 g, 0.8 mmol),
It was reacted with 2d (1.95 g, 8 mmol) at 100° C. for 24 hours. The final polymer yield was 2.51 g. The addition reaction rate of the polymer was 98.5 mol% (N
results of analysis). The reduced viscosity of the polymer in DMF is
It was 0.22 dl/g (measured at 30°C, 0.5 g/dl).
IR (film): 1720, 1590, 1510, 1340, 750 and 710 cm ^-1 , NMR (CDCl ₃ ): δ = 0.9 (C-CH ₃ ),
2.0 (C-CH ₂ -C), 4.3 (C-CH ₂ -O), 5.6 (C
-CH-O) and 6.8-8.2 (aromatic hydrogen). This polymer is poly[2-benzoyloxy-3-
(4-nitrophenoxy)propyl methacrylate] (3d). Example 5 Preparation of poly(2-benzoyloxy-3-thiophenoxypropyl methacrylate) (3e) PGMA (1.16 g, 8 m
2e (1.71 g, 0.8 mmol) and TEAB (0.16
g, 0.8 mmol) 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 mol% (measured from the intensity ratio of NMR spectra). 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): 1720, 750 and 710cm ^-1 , NMR
(CDCl ₃ ): δ = 0.9 (C-CH ₃ ), 1.9 (C-CH ₂ -
C), 3.2 (C-CH ₂ -S), 4.3 (C-CH ₂ -O),
5.3 (C-CH-O) and 7.0-8.0 (aromatic protons). This polymer is poly(2-benzoyloxy-3-thiophenoxypropyl methacrylate) (3e). Example 6 Poly[2-benzoyloxy-3-(4-chlorophenoxy)propyl methacrylate] (3l)
Production of PGMA (1.16 g, 8 mmol) with diglyme (20
ml) in the presence of TEAB (0.16 g, 0.8 mmol),
It was reacted with 2 liters (1.86 g, 8 mmol) at 100° C. for 24 hours.
The final polymer yield was 2.09g. The addition reaction rate of the polymer was 74.3 mol% (as a result of Cl analysis and ¹ H-NMR integrated intensity ratio). The reduced viscosity of the polymer in DMF was 0.23 dl/g (30
°C, measured at a concentration of 0.5 g/dl). IR (Film):
1720, 1600, 1510 and 710 cm ^-1 , NMR (CDCl ₃ ):
δ=1.0(C- _CH3 ), 1.70(C- _CH2 -C), 4.2(C
_-CH2 -O), 5.6 (C-CH-O) and 6.8-8.0 (aromatic hydrogen). This polymer is poly[2-benzoyloxy-3-(4-chlorophenoxy)propyl methacrylate] (3l). Example 7 Poly[2-(4-nitrobenzoyloxy)3
-Phenoxypropyl methacrylate] (3q)
Production of PGMA (1.16 g, 8 mmol) with diglyme (20
ml) in the presence of TEAB (0.16 g, 0.8 mmol),
It was reacted with 2q (1.95 g, 8 mmol) at 100° C. for 24 hours. The final polymer yield was 1.85g. The addition reaction rate of the polymer was 94.3 mol% (N
results of analysis). The reduced viscosity of the polymer in DMF is
It was 1.02 dl/g (measured at 30°C, 0.5 g/dl).
IR (Film): 1720, 1600, 1530, 1350 and 710
cm ^-1 , NMR (CDCl ₃ ): δ = 1.0 (C-CH ₃ ), 2.0
(C-CH ₂ -C), 4.3 (C-CH ₂ -O), 5.6 (C-
CH-O) and 6.90-8.20 (aromatic hydrogen). This polymer is poly[2-(4-nitrobenzoyloxy)3-phenoxypropyl methacrylate]
(3q). Example 8 Same as Example 1 above, PGMA and 4-nitrophenyl 4-nitrobenzoate (2f), methylbenzoate (2g), and ethylbenzoate (2h)
and phenyl acetate (2i) were subjected to an addition reaction. These polymers are poly[2-(4
-Nitrobenzoyloxy)-3-(4-nitrophenyl)propyl methacrylate] (3f), Poly[2-benzoyloxy-3-methoxypropyl methacrylate] (3g), Poly[2-benzoyloxy-3-ethoxypropyl methacrylate]
(3h) and poly[2-acetoxy-3-phenylpropyl methacrylate] (3i). Similarly, PGMA and 2-nitrophenylbenzoate (2j), 2,4-dinitrophenylbenzoate (2k), 2,4-dichlorophenylbenzoate (2m), phenylbenzoate (2n), 4- Methyl-phenylbenzoate (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), poly[2-benzoyloxy-3-(2,4-dinitrophenyl)propyl methacrylate] (3k), and 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), poly[2-(4-chlorobenzoyloxy)-3-phenylpropyl methacrylate] (3r) and poly[2-(4-methoxybenzoyl)-3-phenyl propyl methacrylate] (3s), etc. The results of the addition reaction are shown in Tables 1 and 2. [Table] [Table] [Table] The reaction rate between side chain epoxy groups and active esters in polymers obtained from elemental analysis is
It is in good agreement with the intensity ratio of the NMR spectrum.
This confirms that almost no side reaction between the epoxy group and hydrogen occurred during this reaction. As can be seen from Table 1, PGMA and esters
Addition reactions with 2a, 2b, 2c and 2e can selectively produce the corresponding polymers 3a, 3b, 3c and 3e, respectively, when TEAB is used as a catalyst at 100°C.
In addition, in the reaction with 4-nitrophenyl 4-nitrobenzoate (2f), 60.3 mol% was generated at 100°C for 4 hours.
The corresponding polymer 3f is obtained at a conversion of . In addition, methyl benzoate (2 g) and phenyl acetate (2i) were heated at 100°C for 24 hours to obtain the corresponding polymers 3 g and 3i in yields of 6.7 mol% and 28.4 mol%, respectively, but ethyl benzoate ( Almost no reaction with 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. Example 9 PGMA (1.16 g, 8 mmol) was added to 2d and 2e (1.95
g, 8 mmol) each and diglyme (20 ml)
at 100 °C in the presence of various catalysts (0.8 mmol) in
The reaction was allowed to proceed for 10 hours. The results are shown in Tables 3 and 4. [Table] [Table] [Table] As can be seen from Table 3, when the active ester in the catalyst is 4-nitrophenylbenzoate (2d), in the quaternary ammonium salt, the counter anions are Br ^- , Cl ^- and I In the case of ^- , high catalytic activity is obtained, while in the case of HSO ^- ₄ or ClO ^- ₃ , high catalytic activity is not shown. And the catalytic activity is very strongly influenced by the alkyl chain in the quaternary salt;
TPAB (propyl) and TBAB (butyl) are
It is shown that the series of quaternary ammonium salts containing Br ^-anion has the highest activity. On the other hand, in a series of quaternary ammonium salts containing Cl ^- 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 is more active than tertiary amines such as TEA and TBA. Furthermore, as can be seen from Table 4, when the ester is phenylthiobenzoate (2e), TBAB has the highest activity in the series of quaternary ammonium salts containing Br ^- as a counteranion, while TMAB shows almost no activity. do not have. On the other hand, in the case of the Cl ^-containing ammonium salt series, TEAC shows the highest activity.
The activity of TBAI, TBPB and TEA is significantly reduced in this reaction system. and TBAH, TBAP and
TBA had no activity. Additionally, certain quaternary salts with Cl ^-anions are
In the reaction of thioester compound (2e), Br ^-
It has higher activity than quaternary salts with 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. Effects of the Invention Consisting of an addition reaction product between the side chain epoxy group-containing polymer of the present invention and a benzoate containing a benzotriazole group, nitroaryl group, chloroaryl group, or sulfur element in the molecule, benzotriazole group in the side chain , nitroaryl group, chloroaryl group, etc. is a new polymer, and it can be used as a resin with excellent adhesiveness, photosensitivity, radiation sensitivity, or radiation resistance, and is considered to be an extremely useful resin. I can say it.

Claims (1)

[Scope of Claims] 1. A functional polymer having a repeating structure represented by the following general formula. 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.