JPH02231458A - N-alkenoyl-enamide, and preparation and use thereof - Google Patents

Abstract

NEW MATERIAL: A compound of formula I (wherein R₁ is H or methyl; R₂ is H, a 1-4 C alkyl or a halogen; and R₃ and R₄ are each a 1-4C alkanoyl, a 1-18 C alkoxycarbonyl, benzoyl, phenyl, cyano or carbamoyl provided that R₄ may be H).

USE: Useful for the production of polymers used for an ultraviolet absorber and radiation-curing material such as a textile finish.

PREPARATION: An alkeneamide derivative of the formula: R₁CH=CR₂-CO-NH₂ is reacted with a phenol ether of formula II (wherein R is 1-4C alkyl) in the temp. range of 130-200°C in the presence of an alkanol elimination catalyst (e.g. phenothiazine) to obtain a compound of formula I. A copolymer is formed by radical-polymerizing a compound of formula I in the presence of an inert organic solvent and a polymerization initiator.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel N-alkenoyl enamides, processes for their preparation, their use for the production of new polymers, and radiation-curable materials as UV absorbers or as textile finishes. Concerning the use of the novel polymer in. N-7 lucanoyl enamide is known, for example, from German Patent Publication No. 2718552. This compound can be used for producing acyl amines, producing polymers with amino groups, or producing amino acids. In accordance with the present invention, new N-alkenoyl enamides have now been discovered which can be usefully used in the production of polymers which can be used in radiation-curable materials as UV absorbers and also as textile finishes. The present invention relates to N-alkenoyl enamides represented by the following general formula. In the formula, R. is hydrogen or methyl, R. is hydrogen, CI-C. -alkyl or halogen, R
, Tore and C. independently of each other. -C-oalkanoyl,
C+ Ct*-alkoxycarbonyl, benzoyl,
means phenyl, cyano or carbamoyl, and h can also mean hydrogen. Preferred N-alkenoyl enamides of formula (1) are those in which Rt is hydrogen, methyl or chlorine, and R, and R4
are each independently acetyl, CI-CI. - is N-alkenoyl enamide, which means alkoxycarbonyl, benzoyl, phenyl, cyano or carbamoyl, and R4 can furthermore mean hydrogen. A particularly preferred compound of formula (1) is an N-alkenoyl enamide compound of formula (1) in which Rg means hydrogen or methyl, and R, and R4 independently of each other mean acetyl or ethoxycarponyl. It is de. The N-alkenoyl enamides according to the invention can be produced economically with good yields.

That is, the N-alkenoyl of 2 (1) according to the present invention ~
The method for producing enamide is based on the formula (21 R+ CH=CRt CO NH
! (wherein R, and h have the meanings given above), an alkenamide compound of the formula (wherein R, and R# have the meanings given above and R is C
, -CG-alkyl) in the presence of an alkanol (R O M) elimination catalyst. Alkanol R
Suitable catalysts for OH@M are phenothiazines, which at the same time act as polymerization inhibitors in the temperature range from 130 to 200°C, preferably from 140 to 190°C. The alkenamide compound of formula (2) is known. Formula (3
For example, a portion of the enol ether of
It is known from the specification No. 824121. The new enol ethers can be made by the method described in this US patent. As the enol ether of formula (3), for example, compounds of the following formula are considered: R 1 , R. and R# in the formula have the meanings listed in Table I below.

m The N-alkenoyl enamide of formula (1) according to the present invention can also be produced by the following method. That is, in the presence of an acid binder, an amine of formula (wherein R and R4 have the above-mentioned meanings) is converted to R. -CI -CRzCoHal (wherein R, and R2 have the meanings given above and 11al means bromine or preferably chlorine) with an acid halide. A method similar to this method was developed by L. Claisen in Liebigs Ann.C.
hem. )2 9 7 (1 8 9 7) , 1
It is described on pages 6 to 32. Suitable amines of formula (4) are compounds in which P, and R4 have the meanings given in the following table.

Table ■ Can be used for the production of polymers containing 0 to 99 mol% of structural units of formula ■: As acid halides of formula <5>, for example acrylic acid, methacrylic acid or crotonic acid chloride. This reaction is an exothermic reaction accompanied by the production of hydrochloric acid, and in many cases the reaction is initiated even at room temperature.

The N-alkenoyl enamide of formula (!) according to the present invention can be prepared by radical polymerization at elevated temperature in the presence of an inert organic solvent and a polymerization initiator.
Based on the total polymer, 100 to 1 mol% of the structural unit of the following formula , N
, N-G.C. -C4-alkylamino01C4-
Alkylcarbamoyl, cyano, formyl, N,N-diC+-Co-alkylaminoC. -C. -alkoxycarbonyl, CI-C. -alkanoyloxy, meaning unsubstituted or substituted carbamoyl, 1-pyrolidonyl, 1-imidazolyl, 2- or 4-pyridinyl, or phenyl, and which means hydrogen or methyl. Suitable inert organic solvents include protic and aprotic solvents such as tetrahydrofuran, dioxane, toluene, xylene, ethyl acetate, butyl acetate,
4-butyrolactone, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl glycol acetate, ethyl glycol acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone come into consideration. As suitable polymerization initiators, compounds having a bond that can be homolytically cleaved under the action of heat are considered. Examples include: M Warson (M.
．． Chandler
R) Ltd. (Braintree, UK)
) publication of “Bell Compounds and Bell Salts (P
er-Compounds and Per-Salt
s in Polya+er Processes)''
(1980), pp. 166 et seq. (C.A.9 3.
1980) 205312v); and aliphatic azo compounds such as abbisisobutyronitrile, 4,4'-azobis(4-cyanovalerate ester); )
Such. Polymerization is carried out at a temperature range of 60 to 100°C. As copolymer units of the formula n, vinyl compounds such as those exemplified below come into consideration: acrylic and methacrylic acids, alkyl esters and alkylaminoalkylamides of acrylic and methacrylic acids, styrene, acrylic and methacrylic acids. N-G Cl-C#-
Alkylamino-C+-C*-alkyl esters, acrylamide and methacrylamide, N-monosubstituted acrylamide and methacrylamide, N-di-CI-C#-
Alkylamino C. -C#-alkyl-acrylamide and -methacrylamide, acrylonitrile and methacrylonitrile, acrolein, acrolein derivatives, vinyl acetate, 1-vinylpyrrolidone, 1-vinylimidazole, 2- and 4-vinylpyridine. The subject matter of the present invention also includes polymers obtained by the method of the present invention, ie, polymers according to the formulas (1) and (2) set forth above. These polymers, copolymers and homopolymers, can be used in the following applications: Photocrosslinkable compositions for imaging such as photographic solutions: Photocrosslinkable compositions for forming relief patterns in commercial printing: Photocrosslinkable composition for producing high-resolution resist for use in the field of microelectronics: The present polymer is 27
Ultraviolet curable coatings and coating compositions with high solvent resistance and temperature stability, focusing on having absorption in the wavelength range of 0 to 300 nm; As a UV absorber; as a UV absorber in protective films for greenhouses; and also as a textile finish to impart specific properties to textile fabrics, such as anti-wrinkle and water-resistant properties.

This copolymer enables the production of heat-resistant resist images with particularly excellent resolution. This is because the polymers generally have excellent mechanical properties as well as relatively high glass transition temperatures (Tg). The present invention will be further explained below with reference to Examples. In a round flask, add 252 g of ethoxymethylene-acetylacetone and 1 g of acrylamide.
14.7 g and 1 g of phenothiazine are charged and the mixture is heated to 160° C. with stirring. 1
Evaporation of the desorbed ethanol begins at 40°C. 64.3g
After the ethanol has been distilled, the reaction is stopped (by cooling) and the monomers produced are isolated by distillation. The obtained lettuce product (251 g) was recrystallized from 220 ml of isopropanol to obtain monomer 188 of the following formula.
Obtain g (64% of logical value). Melting point 58.6-59.
8℃. Daishi Group I A round flask was charged with 377.7 g of ethoxymethylene-ethyl acetoacetate, 144.2 g of acrylamide, and 5 g of phenothiazine, and the mixture was
Heat to 0℃. After distilling 84 g of ethanol, the reaction is stopped (by cooling) and the monomers formed are isolated by distillation. After recrystallization from 300 lI1 of isoprobanol, 275 g of monomer of the following formula are obtained, melting point 65.2-66.8°C. xlu11 at 190° C. according to the method described in Example 1.
Ethoxymethylene-malonic acid monodiethyl ester 35
0.5 g of acrylamide, 138.5 g of acrylamide, and 4 g of phenothiazine were reacted. After distilling off 60 g of ethanol, the produced heptanomer was isolated by distillation and recrystallized from 110@l of cyclohexane to obtain 90 g of the monomer of the following formula.
(23% of the theoretical value). Melting point after redistillation: 46.2-47.2°C. 217. of ethoxymethylene-acetoacetic acid ethyl ester at 155° C. according to the method described in Example 1.
6g and 9 of methacrylamide 9. 5 g of phenothiazine were reacted with 2.5 g of phenothiazine. Monomer 1 of the following formula
71 g (65% of theory) was obtained. Melting point: 68.5-69.8°C Melting point: 25.5°C Similarly, the following 1,000 nomer was obtained: Melting point: 66. 3-68. 5℃ Melting point: 46.8-47.9℃ Melting point: 33.2-34.7℃ Melting point: 90.4-91.9℃ Charge 18.75 g of Nomer, 0.02 g of t-butyluberoxy-2-ethylhexanoate, and 28 g of dioxane. After introducing nitrogen for 10 minutes, heat the mixture to 82°C. Polymerization begins at 77°C with an exothermic reaction, and after 90 minutes it becomes slightly cloudy. After 2 hours, the reaction was stopped by cooling,
Dilute the slightly cloudy, viscous solution with 35 l of dioxane. When this solution is poured into ethanol, the homopolymer precipitates. Therefore, 0.32d 1 in dioxane
17.1 g (91% of theoretical value) of homobolima with reduced viscosity of
) is obtained. The operation was carried out in the same manner as in Example 5. However, this time the formula (1
00), 0.2 g of didodecanoyl peroxide and 4'ltml of tetrahydrofuran were used. After purging the air with nitrogen, the mixture was heated to 67° C. with stirring for 20 hours. The solution became slightly cloudy and viscous. After cooling, the solution was poured into ethyl alcohol to precipitate the homopolymer. This precipitate was dried and dissolved in acetone at 0.10 dj! /g (c=
Homopolymer-3 with a reduced viscosity of 0.5% g/V)
8. 2 g (97.4% of theory) were obtained.

The operation was carried out in the same manner as in Example 5. However, this time the formula (1
00), 6 g of acrylic acid ethyl ester, and 0.1 g of t-butyl peroxy-2-ethyl hexanoate were used. After purging the air with nitrogen, the mixture was heated to 76° C. for 5 hours with stirring. After cooling, this solution was poured into ethyl alcohol to precipitate the copolymer. The precipitate was dried to 0.41 dl/g (c - 0.5%) in acetone.
28.8 g of a polymer consisting of 70 mol % of the monomer of formula (100) and 30 mol % of acrylic acid ethyl ester and having a reduced viscosity of (g/V) was obtained. The operation was carried out in the same manner as in Example 5. However, this time the formula (4
01) monomer 16.5g. Acrylic acid 1.1g, t
0.04 g of -7'' thiruberoxy-2-ethylhexanoate and 26 g of dioxane were used. After purging the air with nitrogen, the mixture was heated to 82° C. for 3 hours and 15 minutes with stirring. After cooling, the solution was poured into ethanol to precipitate the copolymer. The precipitate was dried and dissolved in acetone at 0.28 dl/g.
Equation (4) with reduced viscosity of (c = 0.5% g/V)
01) monomer 84.6 mol% and acrylic acid 15.4
14 g (79.5% of theory) of a polymer consisting of mol%
I got it. By a similar method, the following formula (in the formula, R. is hydrogen, R, and Ra are -COCH:l
, and Rt has the meaning given in Table 1), and optionally the comonomer acrylic acid (A
), acrylic acid ethyl ester (B) or styrene (
The following polymer was produced from C). Table 1 *C = 0 in acetone. Measured at 5% g/v.
Shio 1 for Juhachi: Ethyl acetate for numbers 1, 3 and 4, dioxane for positive 2, 5 and 7, toluene for positive 6.

In a reaction vessel equipped with a main stirrer, a condenser, and a thermometer, 30 g of the monomer of formula (200), 14.2 g of acrylic acid ethyl ester, and t-butyl peroxy-2-ethyl hexanoate were added. 0. Charge 15 g and 100a+42 of ethyl acetate. Heat this mixture to 75°C for 4 hours with stirring. After removing the solvent, the resulting copolymer was taken out into acetone. Pour this solution into water to precipitate the polymer. However, the formula (20
41.1 g (92.7% of theory) of a copolymer consisting of 50 mol% of the monomer units of 0) and 50 mol% of acrylic acid ethyl ester was obtained. The operation was carried out in the same manner as in Example 9. However, this time, the formula (2
00) monomer 23.8g. 3.4 g of dimethylaminopropyl-methacrylamide. 0.06 g of t-butyl peroxy-2-ethyl hexanoate and 40 g of dioxane were used. The mixture was heated to 83° C. for 5 hours with stirring. Another 0. After adding 0.6 g of t-butyluberoxy-2-ethylhexanoate, fHJft coalescence was carried out at 83° C. for 14 hours. After cooling, the reaction solution was poured into ethyl alcohol to precipitate the copolymer. Thus, a copolymer 11.2 consisting of 85 mol% of monomer units of formula (200) and 15 mol% of dimethylaminopropyl-methacrylamide
g (41% of the theoretical value). By a similar method, a monomer of formula (500) (R in the formula
1 is hydrogen, Rco is -COCL, R# is -COOCtH%
and h has the meaning given in Table 1) and, in some cases, comonomers (A) or (C) to produce the following polymers. In acetone, C-O. S% Measured in g/v.
f0 for humans: Tetrahydrofuran for positive 8, ethyl acetate for negative 9 and l3, dioxane for negative 10, l2, l4 and 15, toluene for magnetic 11. The same procedure as in Example 9 was carried out. However, this time the formula (3
00) heptanomer 20.4g, acrylic acid 1. 1g,
0.0 of t-butyl peroxy-2-ethyl hexanoate. 04 g and 32 g of dioxane were used. The mixture was heated to 82° C. for 2.5 hours with stirring. After cooling, the solution was poured into water to precipitate the copolymer and 0.3 d in acetone (c=0.5% g/V)
Heptanomer 84 of formula (300) with reduced viscosity of l/g
．． 20. of a copolymer consisting of 6 mol % and 15.4 mol % acrylic acid. 5 g (95.3% of theory) was obtained. By a similar method, the homopolymers shown in the following table were obtained from monomers 2 (500) in which R and R2 are hydrogen and R and R4 are one COOCJs. Table 2-1- * In acetone, c = 0. Measured at 5% g/v.
Clear! Tetrahydrofuran for So3ke'2MU Ray11hl6, ethyl acetate for Nal7, and dioxane for No.18. Similarly, R, is methyl, R2 is hydrogen, and R, and R. The following polymer was obtained from a monomer of formula (500) in which `` and '' have the meanings listed in the following table (■) and a comonomer vinyl acetate (E). Table ■ Book In acetone, c = 0. Measured at 5% g/v.

Riki Fuu Friendship ■ Boarding Dioxane. 50a equipped with stirrer, thermometer, reflux cooling (outlet blocked with bubble counter sealed with light paraffin)
ef capacity flat polished flask, add 15.0 g of acrylamide methylene acetylacetone. 3.8 g of N-tert-butylacrylamide, 2.7 g of acrylic acid,
t-Butyloperoctoate (10% in dioxane)
1.0 g and 31.0 g of dioxane. The monomer content of this solution is 40.2%. After careful purging with Nt, the flask contents were brought to an internal temperature of 80°C.
Heat while stirring until . A polymerization reaction occurs with intense heat generation, and the internal temperature rises to 105°C. After 30 minutes, dilute the reaction mixture with 5 μl of dioxane and add 80 μl of dioxane.
Polymerization was completed at ℃ for 5 hours. This yields a highly viscous, transparent solution. After diluting this solution with dioxane again, pour it into water to precipitate the polymer. Drying the precipitate gives 20.6 g (95.8% of theory) of colorless cobolimer with a softening point above 200° C. and a reduced viscosity of 0.73 dl/g in dioxane. The operation was carried out in the same manner as in Example 12. However, this time, f5.0g of acrylamide methylene-acetylacetone,
3.5 g, t of N-methyl-N-vinylacetamide
-petit ruber octoate (10% in dioxane) 0
．． 7g and 2 of dioxane 7. 0 g was used. The monomer content of this solution is 40% by weight. Carefully N. After purging with water, the batch was heated with stirring to an internal temperature of 80°C. A polymerization reaction occurred with intense heat generation, and the internal temperature rose to 98°C. 20III! The reaction mixture was diluted with dioxane and the polymerization was completed at 82° C. for 5 hours. The resulting slightly yellow colored, highly viscous, clear solution was further diluted with dioxane and then poured into water. The precipitate was dried to yield 17.8 g of a substantially colorless cobolimer with a softening point of 200° C. (theoretical value of 9
6.2%). After drying, this material lost its solubility in dioxane and in DMA and could only swell strongly.

Missed soil↓ The operation was carried out in the same manner as in Example 12. However, this time, 10.0g of acrylamide methylene-acetylacetone,
2.9g of styrene. 2. Acrylic acid ethyl ester.
8 g, t-butyrubel octoate (1 in dioxane)
0%) 0.7g and 2 of dioxane 3. 0 g was used. The monomer content is 39.9% by weight. After careful purging with Nt, the batch was heated with stirring to an internal temperature of 80°C. It was held at this temperature for 5 hours, then diluted with dioxane and poured into water to precipitate the polymer. However, the softening point is 158°C and the reduced viscosity is 0.72d! 15.0 g (95.5% of theory) of colorless cobolimer of 15.0 g (95.5% of theory) were obtained (in dioxane). The procedure was carried out analogously to Example 12. However, this time we will discuss 11 of acrylamide methylene-acetoacetic acid ethyl ester.
．． 1 g, 0.85 g of acrylonitrile, 1.3 g of N-vinylpyrrolidone (2). ．． t-petite ruber octoate (10% in dioxane) 0. 4 g and 2 of dioxane 4. 0 g was used. After careful purging with N, the batch was heated with stirring to a temperature of 80°C. Even after the exothermic polymerization reaction subsides, 5 more
The resulting highly viscous clear solution was diluted once more with dioxane and poured into water to precipitate the polymer. The precipitate was dried to obtain 12.2 g (92% of theory) of colorless cobolimer with a softening point of 170 DEG C. and a reduced viscosity of 0.93 dl/g (in dioxane). The operation was carried out in the same manner as in Example 12. However, this time, 13 of acrylamide methylene-acetoacetic acid ethyl ester
．． 2.0g,N~methoxymethyl-methacrylamide.
0 g, t-butyl peroctoate (1 in dioxane)
0%) and 27.0 g of dioxane were used. The 1,000-mer content of this solution is 35.4% by weight.

After purging with N2, the mixture was heated with stirring to an internal temperature of 80°C. After the exothermic polymerization reaction had subsided, the mixture was kept at 80°C for another 5 hours, then diluted once again with dioxane, and poured into water to precipitate the polymer. The precipitate was dried to obtain 14.4 g (96% of theory) of colorless cobolimer with a softening point of 158 DEG C. and a reduced viscosity of 0.3 dl/g (in dioxane). The operation was carried out in the same manner as in Example 12. However, this time, 13 of acrylamide methylene-acetoacetic acid ethyl ester
．． 0g, 1.3g of vinyl acetate. 0.4 g of t-butyl peroctoate (10% in dioxane) and 4 g of dioxane 7. 0 g was used.

The monomer content of this solution is 23.2% by weight.

After carefully purging with N8, polymerization was carried out at 80°C for 2 hours.
The resulting clear viscous solution was diluted with dioxane and then poured into water to precipitate the polymer.

The precipitate was dried to have a softening point of 165°C and a reduced viscosity of 0.
13.2 g (92.3% of theory) of a colorless copolymer with a yield of 2 6 dl/g (in dioxane) were obtained.

x1111 8 The operation was carried out in the same manner as in Example 12. However, this time, 20.0g of acrylamide methylene-acetylacetone.
10.7g of stearyl methacrylate, N-tert
-2.0 g of butylacrylamide. 0.1 g of t-butyl peroctoate and 60 g of dioxane were used. The monomer content of this solution is 35% by weight.
After careful purging with N, the batch was brought to an internal temperature of 80
The mixture was heated to ℃ while stirring. After holding at this temperature for a further 4.5 hours, the resulting slightly yellow colored clear viscous solution was diluted with 50 ml of dioxane and poured into water to precipitate the polymer. However, the softening point is 97℃
, the reduced viscosity is 0. 31.9 g of colorless copolymer with 38 dl/g (in dioxane) (97.9 g of theoretical value).
2%). 12.0 of airacrylamide methylene-acetylacetone on expectoration plaques
g, 0.9 g of acrylonitrile. 28.0 g of stearyl methacrylate, o. Weigh 1 g and 65 μl of dioxane and charge them into the reactor. Its monomer content is 38% by weight. After careful purging with N, the batch is heated with stirring to an internal temperature of 80° C. and polymerization is carried out at this temperature for a further 5 hours. The resulting yellow colored transparent viscous solution was further diluted with dioxane and poured into 2J water to precipitate the polymer. Softening point is 55℃
, the reduced viscosity is 0. 40 g of a colorless copolymer of 4 2 dl/g (in dioxane) (theoretical value of 97.5
%) was obtained. 12.0 of acrylamide methylene-acetylacetone
g. 1.8g of acrylonitrile. 22.4 g of stearyl methacrylate. 0.1 g of t-butyl peroctoate and 60 ssl of dioxane are sequentially weighed and charged into the reactor. The monomer content is 37% by weight. After careful purging with N2, the batch is heated with stirring to an internal temperature of 80° C. and polymerization is carried out at this temperature for a further 5 hours. The resulting yellow colored transparent viscous solution was further diluted with dioxane and poured into 2 liters of water to precipitate the polymer. 34.8 g (96% of theory) of a colorless copolymer with a softening point of 60° C. and a reduced viscosity of 0.55 dl/g (in dioxane) are obtained. A coating solution with the following composition was prepared: Polymer 3 of Table 1 1.゛5 g4-butyrolactone
10.0 g Wetting agent based on perfluorocarboxylic acid e.g.
Company M's Fluorad ■FC4300.
001g. Spread this solution onto a copper-laminated epoxy resin board to a thickness of 1
It was applied to 2μ using a coating blade. The coating was dried for 2.5 hours at 60° C., an optical mask (Stouffer optical wedge) was placed on the plate and exposed for 300 seconds with an IOOOW UV lamp from a distance of 18 mm. After this, I developed the board. As a result, the lowest clear mapping level was 9. A large piece of cotton cretone was impregnated with a treatment bath having the following composition, squeezed to 100% pick-up, and dried at 60°C for 4 hours. Bath (A) Polymer of Example 12, 13, 15, 16 or 17
100g dioxane 900g sensitizer
0.01g. Bath (B) Polymer of Example 12, 13, 15, 16 or 17
100g dioxane 900g sensitizer
0. Olg photoinitiator
0.05g. The treated cretone samples were tested for textile finish properties. The test was conducted on the dried sample as follows. a) Extraction twice with dioxane; b) 5000 W UV lamp (Staub, Neu-Isenburg, West Germany);
Staub product] from a distance of 801 to one side of the sample.
C) Perform irradiation as in b) above, then extract twice with dioxane, and then measure the Nt content (%). The test results are summarized in the following table ■. Kazuichi Taka! Umbrella Elemental Analysis Umbrella This sample is not extracted, soap 5 g / l
and 2 g/l of sodium carbonate in a bath ratio of I:40 at 95°C for 20 minutes and then dried. 1 Mixing ratio 3 3/6 7 cotton/diale
n) Impregnating the mixed fabric (210 g/of) with a bath containing the following components and squeezing to a surprise up of 80%,
It was then dried at 60°C. Polymer of Example 18 50g dioxane
950g sensitizer
0.01g.

The dried fabric treated above was irradiated on both sides as described in Example 22 and extracted twice with dioxane to remove unreacted polymer. Size 20X25c
A sample piece of m was conditioned at 20° C. and 65% relative humidity and weighed (this weight is referred to as weight i1A).

After this, the specimen was subjected to a spray test. In this test, the specimen is held between two clamps, and
Spray with 500 ml of water at °C. Then, pull it strongly in the longitudinal direction three times to remove any water droplets that may have adhered to it.

After this, hold the test piece in both the vertical and horizontal directions and shake it vigorously three times each. Then weigh the sample piece (
This weight is called weight B). Determine the amount of water absorbed from the two weights A and B. (For absorption comparison, the same test was also carried out on unfinished fabric samples, and on fabric samples that were finished but not irradiated.

The test results are summarized in Table Vl. What is the bending stiffness of this treated sample? l DI38B-
Measured using the test method specified in 647. For comparison, the same tests were also conducted on fabric samples without finishing treatment and on fabric samples that were finished but not irradiated. The test results are summarized in Table ■.

A cotton cretone cloth (135 g/rrf) was impregnated with a bath containing the following ingredients, squeezed to a 85% kick-up, and dried at 60°C. Polymer of Example 14 50g dioxane
950g sensitizer
o. oig. The treated and dried fabric was irradiated on both sides as described in Example 22 and extracted twice with dioxane to remove unreacted polymer. *
The larger the number, the greater the bending stiffness of the sample.

叉子桝lΣ Processing was carried out as described in Example 23.

However, this time, a cotton/polyester fabric (290 g/rrf) with a mixing ratio of 33/67 and a bath with the following composition were used. Polymer of Example 1B 100g dioxane
900g sensitizer
0.02g. The fabric treated as described above is D I
Water impermeability was tested using the test method specified in No. 53886. For comparison, the same tests were also carried out on unfinished textile samples and on textile samples that were finished but not irradiated. Water impermeability is expressed in water column values.

The test results are summarized in Table ■. Sue's father-in-law

Claims (1)

[Claims] 1. Formula (1)▲ Numerical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is hydrogen or methyl, R_2 is hydrogen, C_1-C_4-alkyl or halogen, R_3 and R_4 are mutually independently C_1-C_4
N-alkenoyl-enamides of -alkanoyl, C_1-C_1_■-meaning alkoxycarbonyl, benzoyl, phenyl, cyano or carbamoyl, and R_4 may also mean hydrogen). 2. In the formula, R_2 is hydrogen, methyl or chlorine, R_3 and R_4 are independently acetyl, C_1-C_1_
2. N-Alkenoyl-enamide according to claim 1, in which .sup.-alkoxycarbonyl, benzoyl, phenyl, cyano or carbamoyl is meant, and R_4 may furthermore be hydrogen. 3, R_2 in the formula means hydrogen or methyl, R_3
N-alkenoyl- according to claim 2, wherein and R_4 independently of each other represent acetyl or ethoxycarbonyl.
Enamide. 4. Formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 is hydrogen or methyl, R_2 is hydrogen, C_1-C_4-alkyl or halogen, R_3 and R_4 are independently
-alkanoyl, C_1-C_1_■-alkoxycarbonyl, benzoyl, phenyl, cyano or carbamoyl, and R_4 can furthermore mean hydrogen),
The alkenamide derivative of the formula R_1CH=CR_2-CO-NH_2 (in the formula, R_1 and R_2 have the above-mentioned meanings) can be expressed by the formula ▲ Numerical formula, chemical formula, table, etc. ▼ (in the formula, R_3 and R_4 have the above-mentioned meanings) has a meaning and R
means C_1-C_4-alkyl) in the presence of an alkanol elimination catalyst. 5. The method according to claim 4, characterized in that a phenothiazine is used as a catalyst. 6. Process according to claim 5, characterized in that the reaction is carried out in a temperature range of 130 to 200°C, preferably 140 to 190°C. 7. The N-alkenoyl enamide produced by the method according to claim 4 is subjected to radical polymerization at elevated temperature in the presence of an inert organic solvent and a polymerization initiator to form the following formula on the basis of the total polymer: 1 structural unit of I
00 to 1 mol% and 0 to 9 structural units of the following formula II
Method for producing a polymer containing 9 mol%: (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1, R_2, R_3, R_4 has the meaning according to claim 4, R_5 is carboxy, C_1-C_1_■-alkoxycarbonyl, N,N-di-C_1-C_4-alkylamino-C_1-C_4-alkylcarbamoyl, cyano, formyl, N,N -di-C_1-C_4-alkylamino-C_1-C_4-alkoxycarbonyl, C_1
-C_4-alkanoyloxy, unsubstituted or substituted carbamoyl, 1-pyrrolidonyl, 1-
imidazolyl, 2- or 4-pyridinyl, or phenyl; R_6 means hydrogen or methyl). 8. Process according to claim 7, characterized in that ethyl acetate, tetrahydrofuran or dioxane is used as solvent for the polymerization. 9. Tert-butylperoxy-2 as a polymerization initiator
9. Process according to claim 7, characterized in that - ethylhexanoate or didecanoyl peroxide is used. 10. The method according to any one of claims 7 to 9, characterized in that the polymerization is carried out in a temperature range of 60 to 100°C. 11. 1 structural unit of the following formula I based on the total polymer
00 to 1 mol% and 0 to 9 structural units of the following formula II
Polymer containing 9 mol%: (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 is hydrogen or methyl, R_2 is hydrogen, C_1-C_4-alkyl or halogen, R_3 and R_4 independently of each other C_1-C_4
-alkanoyl, C_1-C_1_■-alkoxycarbonyl, benzoyl, phenyl, cyano or carbamoyl, and R_4 may furthermore mean hydrogen, R_5 is carboxy, C_1-C_1_■-alkoxycarbonyl, N,N-di- C_1-C_4-alkylamino-C_1-C_4-alkylcarbamoyl, cyano, formyl, N,N-di-C_1-C_4-alkylamino-C_1-C_4-alkoxycarbonyl, C_
1-C_4-alkanoyloxy, unsubstituted or substituted carbamoyl, 1-pyrrolidonyl, 1
-imidazolyl, 2- or 4-pyridinyl or phenyl, R_6 means hydrogen or methyl). 12. A photocrosslinkable composition for use in photographic solutions or UV-curable coatings, characterized in that the composition contains the polymer according to claim 11. 13. A fiber finishing agent for imparting wrinkle resistance and water resistance, characterized in that the finishing agent contains the polymer according to claim 11.