United States Patent 119 Gensho et al. im 4,192,684 (45) Mar, 11, 1980 [54] PHOTOSENSITIVE COMPOSITIONS CONTAINING HYDROGENATED 1.2-POLYBUTADIENE [75] Inventors: Takahashi Gensho; Yanai Masamitsu; Korihara Masakary; Tanaka YYonchar, Srvoki Karahi, al of Fa Japan 173] Assignee: Asahi Kast Kogyo Kabushiki Kish, naka, Japan (21) Appl. No 898258 [22] Filed: Apr. 20, 1978 Related US, Applicaton Data [63] Comino of Sr.No, 760.21, 7,197, aba Sone [30] Foreign Application Priority Data Jan, 24,1976 [BF] Japan suet [51] Int. 2 Gasc 1/68 [2] Us.a. 130/284; 204/159.15; "2047139.19; 430/285, 430/281 [58] Feld of Search 96/115 R, 115 P; 204/159.15, 159.19 156] References Cited US. PATENT DOCUMENTS: 3855379 12/1974 Araki eta. 2041919 Soon ors 1/1977 Barzysl etal cnn 96/115 R 4004997 1/1977 Teskamoto et an 96/115 R 423993 S/A9TT Imaizumi eal nono 96/115 R Primary Beaminer—Iack P. Brammer Attorney, Agent, or Firm—Sprung, Felfe, Hora, Lynch, & Kramer (1 ABSTRACT ‘A photosensitive composition comprising: (a prepolymer having terminal ethylenically unsat- urated groups and 2 number average molecular ‘weight of about 2,000 to 30,000 whose main seg- ment is @ a residue of a hydrogenated 1,2- polybutadiene having about 1.2 to 20 terminal hydroxy groups as average per molecule and a hydrogenation ratio of pendent vinyl groups of the 1,2.addition units of about $0 to 100 percent, (i) a residue of a chain extended hydrogenated 1,2- polybutadiene having 2 to 20 urethane bonds ob- {tained by reaction between the hydrogenated 1,2- polybutadiene and diisocyanate, (i) a residue of a hydrogenated 1,2-polybutadiene having terminal ‘carboxyl groups obtained by reaction between the hydrogenated 1,2-polybutadiene and a dicarbox- yiic acid of (v)'a residue of a chain extended hy- drogenated 1,2-polybutadiene having terminal car- boxy] groups obtained by reaction between a chain extended hydrogenated 1,2-polybutadiene having terminal hydroxy groups and 2 to 20 urethane ‘bonds having been prepared by reaction between the hydrogenated 1,2-polybutadiene and the diso- cyanate, and a dicarboxylic acid, (1) at least one polymerizable ethylenically unsaturated com- pound, (III) a photopolymerization initistor, and (IV) a stabilizer, useful in the preparation of relief image, especially flexographic printing plates hav- ing superior resistance to solvent type flexographic {nk and mechanical properties. 28 Claims, No Drawings4,192,684 1 PHOTOSENSITIVE COMPOSITIONS ‘CONTAINING HYDROGENATED 412-POLYBUTADIENE ‘This is a continuation of application Ser. No. 760,211, filed Jan. 17, 1977, now abandoned. BACKGROUND OF THE INVENTION This invention relates to novel photosensitive compo- 10 sitions. More particularly, its concerned with photo- sensitive compositions which are photopalymetizable by the action of actni light and which are useful inthe preparation of relief image, especially reli. printing plates for Nexographic printing having superior resis: {ance to solvent type Mlexographic ink and mechanical Properties “Many prior art references teach various photoseasi- tive compositions useful in the preparation of relief printing plates. ‘The exographic printing plates ob- {ained from unsaturated polyester type photosensitive compositions disclosed in, for example, Japanese Pat No. 542,085 are insufficient in resistance to solvent type flexographic ink containing organic solvents in- cluding lower allyl alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol exters such as ety acetate and n-butyl acetate; and ketones such a acetone and methylethyl ketone. Japanese Patent Laid. Open 37521/10972 describes photosensitive compositions con- taining a specific block copolymer asa binder and the reli printing plates obtained therefrom having, g00d resistance to alcohol based solvent type Mexographie ink However, these compositions which are solid ‘would be economically disadvantageous in order 19 Provide variety ofthe photosensitive elements in 26- Cordance with their we conditions such asthe thickness Of flexographic printing plates slected, usally from about 04 mm. to 10 mm. and the printing machine employed. The flexographic printing plates obtained from the’ photosensitive compositions containing a 40 polyester-polyether block polymer described in British Pat: No. 425,274 have improved mechanical proper- ties and printing durability but their ink resistance 10 solvent type flexographic aki stl not enough. ‘THE INVENTION According to this invention there is provided a pho- tosensitive composition comprising: ‘@) 100 parts by weight of one prepolymer having terminal ethylenically unsatursted. groups and number average molecular weight of about 2000 {to 30,000 whose main segment is () a residue of a hydrogenated 1,2-polybotadiene having about 1.2 0 20 terminal hydroxy groups as average per molecule and-a hydrogenation ratio of pendent Vinyl groups ofthe 1 2-adlition units of bout 0 100 percent, (i) a residue ofa chain extended hy- Arogenated',2-polybutadiene having 2 to 20 ure- thane bonds obtained by reaction between the hy- Arogenated 12-polybutadiene and a disooyanate, Gil residue of hydrogenated 12-polybutadiene hhaving terminal carboxyl groups obained by reac: tion between the hydrogenated 1,2-polybutadiene and a dicarboxylic acid or (iv) residue ofa chain extended hydrogenated 12polybutadiene having terminal carboxyl groups obtained by reaction between a chain extended hydrogenated. 1,2- polybutadiene having terminal hydroxy groups and 20 2s 0 3s 4 so “ 2 2 to 20 urethane bonds having been prepared by reaction between the hydrogenated 1,2-polybut ene and the diisocyanate, and a dicarboxylic acid, (UD about 5 to 100 parts by weight of at least one polymerizable ethylenically unsaturated mono- ‘metic compound, (UID « photopolymerization initiator in an amount of about 0.001 0 10 weight percent of the total ‘weight of the prepolymer (I) and the polymerizable ethylenically unsaturated monomeric compound (Wy and IV) & stabilizer in an amount of about 0.001 to 2.0 ‘weight percent of the total weight ofthe prepoly- mer (1) and the polymerizable ethylenically unsatn- rated monomeric compound (I) ‘The photosensitive compositions according to this invention are liquid and have a suitable viscosity from the viewpoint of processability. ‘The hydrogenated 1,2-polybutadienes which may be employed in the preparation ofthe prepolymers in this invention mean 1,2-polybutadienes in which at Teast about 50 percent of pendent vinyl groups of the 1,2- addition units are hydrogenated and poly-I-butenes. ‘The hydrogenation ratio greatly affects the mechanical properties of photopolymerized articles. When the hy- Grogenated 1,2-polybutadiene having a hydrogenation ratio of less than $0 percent is employed the rubber elasticity of flexographic printing plates obtained there- from is reduced and the hardness becomes higher, and accordingly good printing quality cannot be produced. ‘Also the hydrogenated 1,2-polybutadienes according + to this invention have at least about 1.2 and preferably 1.5 to 2.0 terminal hydrony groups a average per mole- cule. Whea the average number of terminal hydroxy fr0up per molecule is below 1.2, there cannot be ob- tsined Mesographic printing plates having sufficient mechanical strength. On the other hand, when the aver- age number of terminal hydroxy groups per molecule increases to 2, the elongation and especially the me- chanical strength are more improved. ‘The hydrogenated 12-polybutadienes according to this invention may contain 0 to about 20 percent of Léaddition units. ‘These hydrogenated 12-polybutadienes having. at least about 1.2 terminal hydroxy groups may be either commercially avaiable ones or those produced by con- ‘ventional methods. For example, one method comprises subjecting butadiene to anion polymerization, adding cthylene oxide to the texminal of the eslting polybu- tadiene to give terminal hydroxy groups and subse- quently hydrogenating the pendent vinyl groups ofthe I:2adaition units Another method comprises polymes- izing butadiene using a metal salt such at NaPdCly KPaCle, NHsPACI or PaBrzas a polymerization initia: tor, introducing hydroxy groups tothe terminals ofthe resulting polybutadiene and hydrogensting the vinyl groups of the 12-addition unit. Stil otfer method ‘Comprises subjecting Lbutene to radical polymerization using a peroxide oF az0 compound having a hydroxy {group such as ter-bulyl@-hydronyethyl peroxide oF 44'azobis-Leyano-a-amy) aleohol to produce poy-I- bitenes having terminal hyGrony groups. ‘The prepolymer having terminal polymerizable eth- ylenically unsaturated groups which may be employed in this invention include the folowing five types of prepolymer: ‘The prepolymers (I) may be prepared by effecting reaction between the hydrogenated 12-polybutadienes4,192,684 3 ‘having terminal hydroxy groups and (@) a carboxylic acid or dicarboxylic acid having 3 10 5 carbon atoms ‘and one ethylenically unsaturated group, its anhydride, its chloride or the dicarboxylic acid monoester of a Tower alkyl alcohol having Ito 3 carbon atoms. Exemplary carboxylic acids, dicarborylic acids, an- hydrides, chlorides and monoesters (a) include acrylic acid, methacrylic acid, acrylic anhydride, methacrylic anhydride, acrylic chloride, methacrylic chloride, ita- ‘conic anhydride, monomethyl, monoethyl, mono-n- ‘propyl or monoisopropyl ester of itaconic acid, mono ‘methyl, monoethyl, mono-n-propyl or monoisopropy! ‘ester of maleic or fumaric acid. For this reaction any conventional method may be employed, For example, the reaction is carried out in the presence or absence ofan esterification catalyst such as poluenesulfonic acid or sulfuric acid, and a thermal polymerization inhibitor such as hydroquinone at a temperature of about 60° C. to 180* C. in a nitrogen atmosphere. ‘The prepolymers (1) of this invention may be pre- pared by effecting reaction between a chain extended hydrogenated 1,2-polybutadiene whose terminals are hydroxy groups and (a) the earboxylic acid having 3 10 S.carbon atoms and one ethylenically unsaturated group ‘a8 employed in the preparation of the prepolymers (1) by any conventional method asin the preparation of the prepolymer (0. “The prepolymers (II) ofthis invention may be pre- pared by effecting reaction between a chain extended hydrogenated 1,2-polybutadiene whose terminals are ‘soeyanates and (b) an alcohol having one to three eth- ‘ylenically unsaturated groups by conventional methods. For example, the reaction is carried out ata temperature ‘of about 30°C. to 120°C. inthe presence or absence of 3 ‘ catalyst such as dibutytin dilaurate and preferably a thermal polymerization inhibitor such as hydroquinone under a dry air atmosphere. ‘Exemplary alcohols () include: {@).a compound selected from the group consisting of 20 40 i wherein : 0 'R! represents a hydrogen atom or methyl group, RD represents oxycyclohexylene group, I. The catalyst include, for example, tertiary amines such as NN-dimethylbenzyl amine, N,N-dime- thyllaurylamine and triethylene diamine’ (diazabicy- ‘looetane), and organo-heavy-metal compounds soluble im the reaction system such as ferrous acetoacetate, butyltin dilaurate, dibutylin di-2-hexoate, stannous oleate and stannous octoate. ‘When the chain extending reaction is effected in a mole ratio of OH/NCO 1, the terminals of the chain extended hydrogenated 1,2- polybutadienes are hydroxy groups. “Exemplary diisocyanates which may be employed in the preparation of the chain-extended hydrogenated L2-polybutadienes include 2,t-tolylene disocyanate, 2Gtolylene diisocyanate, hydrogenated 24-tolylene diisocyanate, hydrogenated 2,6olylene diisocyanate, m-phenylene diisocyanate, p-phenylene disocyanate, 1,3+dimethylphenyl-2,4diisocyanat,3-dimethylphe- nyl4,6clisocyanate, 1,¢-dimethyl phenyl-2,Siisocya- hate, I-chlorophenyl-2¢-ditsocyanate, 44-diphenyl isocyanate, 3,3'-dimethyl-44'diphenyl diisocyanate, 2A-diphenyi "isocyanate, 3,3°dimethoxy-4 diphenylmethane isocyanate, —'3,3-dimethyl-44’- ‘phenylmethane diisocyanate, 44”-diphenylmethane isocyanate, —L4-naphthylene ‘isocyanate, 15+ naphthylene diisocyanate, 2,6-naphthylene diisocynate, 2,T-naphthylene diisocyanate, p-xylylene diisocyanate, mexylylene disocyanate, 1,¢-tetramethylene diisocy hate, I Spentametiylene disoyanate, | ¢hexamethy- Tene diisocyanate, 1,7-heptamethylene discyanate 1 ‘octamethylene disocyanate, 1,9-nonamethylene diiso- cyanate, 1,10-decamethylene diisocyanate, 2,2,4- ‘wimethyl-1,S-pentamethylene diisocyanate, 2,2 imethyl-,5-pentamethylene diisocyanate, 3-methoxy- LGhexamethylene diisocyanate, 3-butoxy-1,6-hex- methylene diisocyanate, «,a'-dipropylether diisocya- nate, Is-eyclohexyl disocyanate, 1,3-cyclohexy|diiso- foyanate and mixtures of these diisocyanates "The number average molecular weight of the pre- polymer andthe total number of urethane bonds which fre present in the chain extended hydrogenated 1,2- butadiene affect the properties of photopolymerized articles. According to this invention the number aver- ‘age molecular weight of the prepolymer isin the range (of from about 2,000 to 30,000, and preferably 2,500 to 25,000. When the number average molecular weight is ‘below 2,000, especially the rubber elasticity among ‘mechanical properties ofthe photopolymerized articles is poor for Mlexographic printing plates. On the other hhand, when the number average molecular weight is above 30,000 the rubber elasticity is superior but the 2s 4s 8 6 6 viscosity of the photosensitive composition containing such a prepolymer remarkably increases, and as a result the workability such as processability and developabil- ity of photosensitive compositions diminishes ex- tremely. As the total number of the urethane bonds increases the rubber elasticity ofthe photopolymerized articles becomes improved but the solvent resistance tends to diminish. Thus, the total number of the ure- ‘thane bonds according to this invention isin the range ‘of from 2 to 20 in order to produce flexographic print- ing plates having good balance between rubber elastic. ity and solvent resistance. "Thus, the number average molecular weight of the hydrogenated 1,2-polybutadienes which may be em- ployed inthis invention isin the range of about 1,800 to 29,800, and when chain extended hydrogenated 1,2- ppolybutadienes are prepared the range of the umber average molecular Weights of the hydrogenated 1, polybutadienes is from about $00 to 5,000 and prefera- ‘ly from about 1,000 to 4,000. Examples of suitable polymerizable ethylenically ‘unsaturated monomeric compounds include: (1) Compounds ofthe formula 2 cae! ‘enor? wherein 'R! represents a hydrogen atom or methyl group, 5 represents an alkyl group having 1 to 20 carbon atoms, cyclohexyl, alkoxyalkyl group having at most 15 ‘carbon atoms, cyanoalkyl group having at most 8 car- bon atom, tertiary amino alkyl group having at most 18, carton atoms «hydrogen stom, an orale group CHEHO AH or -HEHD-OF-H wherein R? represents a hydrogen atom, methyl, mono- chloromethyl or mono-bromemethyl group, p repre- sents an integer of 1 to 20, —(CH2\y— OH group ‘wherein q is an integer of 5 to 20, —CHsC(CH2)2C- HOH group or —CHsC(CHaBr),CH0H grou ‘@) Compounds ofthe formula Ve cue xt ‘eon 8 Ne wherein 'R! represents a hydrogen atom or methyl group, RS and RY, each represents a hyrogen atom, alkyl ‘group having 1 to 12 carbon atoms, cyclohexyl, benzyl, ‘=R#_OH in the case of R® being a hydrogen atom, ‘wherein R® represents an alkylene group having 1 to 12 ‘earbon atoms; (@) Compounds ofthe formula