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    • 专利摘要:
    The present invention relates to an oligomer or polymer (A) containing at least one carboxylic acid group in a molecule, at least one compound (B) of formula I, II, III, IV, V or VI, a photopolymerizable reactive or non- (D) as a thermosetting component containing two or more epoxy groups in one molecule. The present invention also relates to a composition suitable as an alkali-developable resist. Formula I (II) (III) Formula IV Formula V VI In the above formulas I to VI, R < 1 > is especially phenyl or alkyl, R 2 is, for example, substituted or unsubstituted C 2 -C 12 alkanoyl, or benzyl, R 3, R 4, R 5 , R 6 and R 7 are each independently, e.g., hydrogen, C 1 -C 12 alkyl, cyclohexyl, or or a substituted or unsubstituted phenyl, benzyl, benzoyl, C 1 - C12 alkanoyl or phenoxycarbonyl, R 8 is, for example, hydrogen, C 1 -C 12 alkyl or Group, M is, for example, C 1 -C 12 alkylene, cyclohexylene or phenylene, M 1 is especially a direct bond or C 1 -C 12 alkyleneoxy, Ar is a 5- or 6-membered aromatic heterocyclic ring.
    公开号:KR20010053101A
    申请号:KR1020007014589
    申请日:1999-06-18
    公开日:2001-06-25
    发明作者:오카히데타카；오와마사키；마쓰모토아키라；구라히사토시
    申请人:에프. 아. 프라저, 에른스트 알테르 (에. 알테르), 한스 페터 비틀린 (하. 페. 비틀린), 피. 랍 보프, 브이. 스펜글러, 페. 아에글러；시바 스페셜티 케미칼스 홀딩 인크.；
    IPC主号:
    专利说明:

    TECHNICAL FIELD The present invention relates to a photopolymerizable thermosetting resin composition,
    The present invention relates to a composition comprising an O-acyloxime photoinitiator, and in particular to the use of the composition in imaging technology.
    From US Pat. Nos. 3558309, 4202697, 4255513 and 4590145 it is known that oxime ester derivatives are photoinitiators. Japanese Patent Laid-Open No. 8-27095 discloses a photopolymerization initiator in which 1-phenyl-1,2-propanedione-2-o-benzoyloxime and 1-phenyl-1,2-propanedione- There is disclosed a solder resist ink composition comprising an ethoxycarbonyloxime. In Japanese Laid-Open Patent Publication No. 8-339081, 1-phenyl-1,2-propanedione-2-o-ethoxycarbonyloxime is used in a similar composition.
    In the field of photopolymerization technology, compositions which are particularly suitable as imaging formulations which are reactive, alkali developable, easy to handle and which exhibit good resolution and which can sufficiently meet the industrial requirements relating to properties such as, for example, thermal stability and storage stability, .
    Surprisingly, it has been found that an oligomer or polymer (A) containing at least one carboxylic acid group in the molecule, at least one compound (B) of formula I, II, III, IV, V or VI, a photopolymerizable reactive or non- It has been found that a photosensitive thermosetting liquid composition comprising an epoxy compound (D) containing two or more epoxy groups in one molecule as a curing component exhibits an unexpectedly excellent performance.



    In the above formulas I to VI,
    R 1 is phenyl optionally substituted with one or more C 1 -C 6 alkyl, phenyl, halogen, OR 8 , SR 9 or NR 10 R 11 ; C 2 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, or C 2 -C 20 alkyl optionally interrupted with one or more -O- and / or optionally substituted with one or more hydroxyl groups ; C 2 -C 20 alkanoyl or benzoyl, which is unsubstituted or substituted by one or more C 1 -C 6 alkyl, phenyl, OR 8 , SR 9 or NR 10 R 11 ; C 2 -C 12 alkoxycarbonyl wherein at least one -O- is optionally interrupted and / or optionally substituted with one or more hydroxyl groups; Phenoxycarbonyl optionally substituted by C 1 -C 6 alkyl, halogen, phenyl, OR 8 or NR 10 R 11 ; Or S (O) m - wherein R is unsubstituted or substituted by C 1 -C 12 alkyl, -CONR 10 R 11 , CN, NO 2 , C 1 -C 4 haloalkyl, S (O) m C 1 -C 6 alkyl, C 6 -C 12 aryl, SO 2 OC 1 -C 6 alkyl, SO 2 OC 6 -C 10 aryl or diphenyl-phosphinoyl,
    R 1 together with R 3 or R 1 together with R 7 may form a 5 or 6 membered ring having one or more CO- and / or oxime groups,
    m is 1 or 2,
    R 2 is C 2 -C 12 alkanoyl optionally substituted by one or more halogens or CN; C 3 -C 12 alkenoyl or benzoyl which is unsubstituted or substituted by one or more C 1 -C 6 alkyl, phenyl, halogen, CN, OR 8 , SR 9 or NR 10 R 11, which is a substituent; C 1 -C 6 alkyl or C 2 -C 12 alkoxycarbonyl or phenoxycarbonyl which is unsubstituted or substituted by halogen,
    R 3 , R 4 , R 5 , R 6 and R 7 are each independently hydrogen, halogen, C 1 -C 12 alkyl, cyclopentyl, cyclohexyl or substituted with one or more OR 8 , SR 9 or NR 10 R 11 Unsubstituted phenyl; Benzyl, benzoyl, C 2 -C 12 alkanoyl, C 2 -C 12 alkoxycarbonyl, optionally substituted with one or more -O-, and / or optionally substituted with one or more hydroxyl groups; Phenoxy carbonyl group or OR 8, SR 9, SOR 9 , SO 2 R 9, NO 2, CN, CONR 10 R 11 or NR 10 R 11 group (wherein the substituents OR 8, SR 9 and NR 10 R 11 is phenyl With the additional substituents present on the ring or with one of the carbon atoms of the phenyl ring to form a 5 or 6 membered ring via the radicals R 8 , R 9 , R 10 and / or R 11 ,
    R 8 is hydrogen, C 1 -C 12 alkyl, or -OH, -SH, -CN, C 1 -C 4 alkoxy, C 3 -C 6 alkenoxy, -OCH 2 CH 2 CN, -OCH 2 CH 2 C 2 -C 6 alkyl substituted with COO (C 1 -C 4 alkyl), -OCO-C 1 -C 4 alkyl, -OCO-phenyl, COOH or COO (C 1 -C 4 alkyl); C 2 -C 6 alkyl substituted with one or more -O-; Halogen, C 1 -C 12 alkyl or C 1 -C 4 alkoxy which is unsubstituted or substituted by - (CH 2 CH 2 O) n H, C 2 -C 8 alkanoyl, C 2 -C 12 alkenyl, C 3 -C 6 alkanoyl alkenyl, cyclohexyl or phenyl; Phenyl-C 1 -C 3 alkyl or Si (C 1 -C 8 alkyl) r (phenyl) 3-r ; Or < Lt; / RTI >
    n is from 1 to 20,
    r is 1, 2 or 3,
    R 9 is hydrogen, C 1 -C 12 alkyl, C 2 -C 12 alkenyl, cyclohexyl, or -OH, -SH, -CN, C 1 -C 4 alkoxy, C 3 -C 6 alkenoxy, OCH 2 CH 2 CN, -OCH 2 CH 2 COO (C 1 -C 4 alkyl), -OCO-C 1 -C 4 alkyl, -OCO-phenyl, COOH or COO (C 1 -C 4 alkyl) C 2 -C 6 alkyl; C 2 -C 12 alkyl substituted with one or more -O- or -S-; Phenyl unsubstituted or substituted with halogen, C 1 -C 12 alkyl or C 1 -C 4 alkoxy; Phenyl-C 1 -C 3 alkyl, Lt; / RTI >
    R 10 and R 11 are each independently, hydrogen, C 1 -C 12 alkyl, C 2 -C 4 hydroxyalkyl, C 2 -C 10 alkoxyalkyl, C 2 -C 5 alkenyl, C 5 -C 12 cycloalkyl Alkyl, phenyl-C 1 -C 3 alkyl, C 1 -C 12 alkyl, or phenyl unsubstituted or substituted with C 1 -C 4 alkoxy; Or C 2 -C 3 alkanoyl, C 3 -C 6 alkenoyl or benzoyl,
    R 10 and R 11 form together C 2 -C 6 alkylene optionally interrupted by -O- or -NR 8 -, or by hydroxyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoyloxy or benzoyl form a C 2 -C 6 alkylene which may be substituted with oxy or
    When R 10 is a hydrogen, R 11 is formula Lt; / RTI >
    R 12, R 13, R 14 , R 15, R 16, R 17, R 18 and R 19 each independently represent or more hydrogen, halogen, C 1 -C 12 alkyl, cyclopentyl, cyclohexyl, or one or OR 8, SR 9 or NR 10 R 11 ; Benzyl, benzoyl, C 2 -C 12 alkanoyl, C 2 -C 12 alkoxycarbonyl, optionally substituted with one or more -O-, and / or optionally substituted with one or more hydroxyl groups; Phenoxy carbonyl group or OR 8, SR 9, SOR 9 , SO 2 R 9, NO 2, CN, CONR 10 R 11 or NR 10 R 11 group (wherein the substituents OR 8, SR 9 and NR 10 R 11 is phenyl or the radicals R 8, R 9, with the R 10 and / or R 11 may form a 5- or 6-membered ring) together with one of the with the additional substituents present in the ring or a phenyl ring carbon atom,
    R 15 and R 16 together form ethylene or ethynylene,
    t is 0 or 1,
    M is C 1 -C 12 alkylene, cyclohexylene, phenylene, -COO- (C 2 -C 12 alkylene) -OOC-, -COO- (CH 2 CH 2 O) n -OC- or -CO - (C 2 -C 12 -alkylene) -CO-,
    M 1 is a direct bond or C 1 -C 12 alkyleneoxy optionally interrupted by 1 to 5 -O-, -S- and / or -NR 10 -
    M 2 is a direct bond or C 1 -C 12 alkylene-S- in which 1 to 5 -O-, -S- and / or -NR 10 - are optionally incorporated,
    M 3 is a direct bond or a piperazino group or C 1 -C 12 alkylene-NR 10 - optionally interrupted by 1 to 5 -O-, -S- and / or -NR 10 -
    M 4 is a direct bond or a group represented by -O-, -S-, -SO-, -SO 2 -, -CO-, -CH 2 -, -NR 10 - Lt; / RTI >
    Ar is a 5 or 6 membered aromatic heterocycle optionally substituted with one or more C 1 -C 6 alkyl, phenyl, halogen, OR 8 , SR 9 , NR 10 R 11 , CN, C 2 -C 6 alkanoyl or benzoyl Click ring,
    Except that 1-phenyl-1,2-propanedione-2-o-benzoyloxime and 1-phenyl-1,2-propanedione-2-o-ethoxycarbonyloxime are excluded.
    Substituted phenyl radicals are substituted one to four times, for example one, two or three times, especially two or three times. The substituent present on the phenyl ring is preferably a 4-position or 3,4-position, 3,4,5-position, 2,6-position, 2,4-position or 2,4,6- And is particularly present in the 4-position or the 3,4-position.
    C 1 -C 20 alkyl is linear or branched, for example, C 1 -C 18 alkyl, C 1 -C 14 alkyl, C 1 -C 12 alkyl, C 1 -C 8 alkyl, C 1 -C 6 alkyl Or C 1 -C 4 alkyl, C 4 -C 12 alkyl or C 4 -C 8 alkyl, especially R 1 is C 6 -C 20 alkyl or C 6 -C 12 alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tertiary butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, Decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and icosyl.
    C 1 -C 12 alkyl, C 2 -C 12 alkyl, C 1 -C 8 alkyl, C 1 -C 6 alkyl, C 2 -C 6 alkyl and C 1 -C 4 alkyl C 1 to the number of the corresponding C atoms to which ≪ / RTI > represents the same meaning as given above for < RTI ID = 0.0 >
    C 2 -C 20 alkyl in which one or more -O- is inserted is inserted one to nine times, one to five times, one to three times or one or two times -O-. Two O atoms are separated by two or more methylene groups, i.e., ethylene. The alkyl group is straight-chain or branched. E.g., -CH 2 -CH 2 -O-CH 2 CH 3, - [CH 2 CH 2 O] y -CH 3 ( wherein, y is 1 to 9), - (CH 2 -CH 2 O) A structural unit of 7 CH 2 CH 3 -, -CH 2 -CH (CH 3 ) -O-CH 2 -CH 2 CH 3 or -CH 2 -CH (CH 3 ) -O-CH 2 -CH 3 is produced . Examples of C 2 -C 6 alkyl in which one or two -O- are interrupted include -CH 2 CH 2 -O-CH 2 CH 2 -OCH 2 CH 3 or -CH 2 CH 2 -O-CH 2 CH 3 have. C 2 -C 12 alkyl and -O- are interrupted by C 2 -C 6 alkyl have the same meanings as given above for C 2 -C 20 alkyl up to the corresponding number of C atoms and O atoms.
    C 2 -C 4 hydroxyalkyl means C 2 -C 4 alkyl substituted by one or two O atoms. Alkyl radicals are straight or branched. Examples are 2-hydroxyethyl, 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1 -hydroxybutyl, 4-hydroxybutyl, 3-hydroxybutyl, 2,3-dihydroxypropyl or 2,4-dihydroxybutyl.
    C 5 -C 12 cycloalkyl is, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, in particular cyclopentyl and cyclohexyl, preferably cyclohexyl.
    C 1 -C 4 alkoxy is linear or branched and is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy or tert-butyloxy.
    C 2 -C 10 alkoxyalkyl is C 2 -C 10 alkyl the inserted one O atom. C 2 -C 10 alkyl represents the same meaning as given above for C 1 -C 20 alkyl up to the corresponding number of C atoms. Examples are methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl or propoxypropyl.
    C 2 -C 12 alkanoyl is linear or branched and is, for example, C 2 -C 8 alkanoyl, C 2 -C 6 alkanoyl or C 2 -C 4 alkanoyl, or C 4 -C 12 alkanoyl or C It is 4 -C 8 alkanoyl. Examples include acetyl, propionyl, butanoyl, isobutanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl or dodecanoyl, preferably acetyl. C 2 -C 8 alkanoyl, C 2 -C 6 alkanoyl and C 2 -C 4 alkanoyl have the same meanings as given above for C 2 -C 20 alkanoyl up to the corresponding number of C atoms.
    C 2 -C 4 alkanoyloxy is linear or branched and is, for example, acetyloxy, propionyloxy, butanoyloxy, isobutanoyloxy, preferably acetyloxy.
    C 2 -C 12 alkoxycarbonyl is linear or branched and includes, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, 1,1- But are not limited to, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, dimethylpropoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl, Carbonyl, propoxycarbonyl, n-butyloxycarbonyl or isobutyloxycarbonyl, preferably methoxycarbonyl. C 2 -C 6 alkoxycarbonyl and C 2 -C 4 alkoxycarbonyl have the same meanings as given above for C 2 -C 12 alkoxycarbonyl to the corresponding number of C atoms.
    C 2 -C 12 alkoxycarbonyl in which one or more -O- is interrupted is straight-chain or branched. The number of atoms is 1 to 5, for example, 1 to 4, 1 to 3, 1 or 2. Two O atoms are separated by two or more methylene groups, i.e., ethylene.
    Phenoxycarbonyl is a compound of formula to be. The substituted phenoxycarbonyl radical is substituted one to four times, for example, one, two or three times, especially two or three times. The substituents present on the phenyl ring are preferably the 4-position of the phenyl ring, or the 3,4-position, the 3,4,5-position, the 2,6-position, the 2,4- , Especially in the 4-position or the 3,4-position.
    Phenyl-C 1 -C 3 alkyl is, for example, benzyl, phenylethyl, α-methylbenzyl or α, α-dimethylbenzyl, especially benzyl.
    C 2 -C 20 alkenyl radicals can be mono- or polyunsaturated and are, for example, C 2 -C 12 alkenyl, C 2 -C 6 alkenyl, such as allyl, methallyl, 1,1 2-butenyl, 1, 3-pentadienyl, 5-hexenyl, 7-octenyl or dodecenyl, tetradecenyl, pentadecenyl, hexa Decenyl, octadecenyl and icocenyl, especially allyl.
    C 2 -C 20 alkynyl radicals are, for example, C 2 -C 12 alkynyl or C 2 -C 6 alkynyl, which may be mono- or polyunsaturated and are, for example, ethynyl, propargyl, 1-butynyl, 3-butynyl, 2-butynyl, 5-hexynyl, 7-octynyl or dodecinyl, tetradecynyl, pentadecynyl, hexadecynyl, octadecynyl or eicosinyl.
    C 3 -C 6 alkenoxy radicals can be mono- or polyunsaturated and include, for example, allyloxy, methallyloxy, butenyloxy, pentenoxy, 1,3-pentadienyloxy or 5-hexyl Lt; / RTI >
    C 3 -C 6 alkenoyl may be mono- or polyunsaturated and may be, for example, propenoyl, 2-methyl-propenoyl, butenoyl, pentenoyl, 1,3-pentadienoyl or 5-hexyl It is senoyl.
    C 1 -C 12 alkyleneoxy is linear or branched and is C 1 -C 8 alkyleneoxy, C 1 -C 6 alkyleneoxy or C 1 -C 4 alkyleneoxy, such as methyleneoxy, ethyleneoxy , Propyleneoxy, isopropyleneoxy, n-butyleneoxy, sec-butyloxyxy, isobutyleneoxy, tertiary butyleneoxy, pentylenoxy, hexylenoxy, heptylenoxy, 2,4,4-trimethyl Pentylenoxy, 2-ethylhexylenoxy, octylenoxy, nonylenoxy, decylenoxy or dodecylenoxy.
    C 1 -C 12 alkylene-S- has the same meaning as given for C 1 -C 12 alkyleneoxy except that the O atom is replaced by a sulfur atom.
    C 1 -C 12 alkylene-NR 10 - has the same meaning as given for C 1 -C 12 alkyleneoxy except that the O atom is replaced by -NR 10 -.
    Halogen is fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine, preferably fluorine and chlorine.
    C 6 -C 12 aryl is, for example, phenyl, 1-naphthyl, 2-naphthyl, preferably phenyl.
    Radicals R 10 and R 11 is -O- or -NR 8 with - a case of forming a C 2 -C 6 alkylene optionally inserted, which form a ring with the N atom to which they are bonded. Examples of such rings are morpholino, piperidino, especially morpholino.
    The substituents OR 8 , SR 9 and NR 10 R 11 present in the phenyl ring, together with further substituents present on the phenyl ring, or together with one of the carbon atoms of the phenyl ring, together with the radicals R 8 , R 9 , R 10 and / or R When a 5 or 6-membered ring is formed through 11 , a structure containing 2 or 4 rings (including a phenyl ring) is obtained. For example, .
    When R < 1 > together with R < 3 > or R < 1 > together with R < 7 > form a 5 or 6 membered ring containing one or more CO- and / or oxime groups, Is generated.
    When R < 15 > and R < 16 > together form ethylene or ethynylene, Is generated.
    Ar as a 5 or 6 membered heterocyclic ring contains O, S or N atoms as a heteroatom and is, for example, furyl, thienyl, pyrrolyl, oxinyl, dioxinyl or pyridyl. The heterocyclic ring may be substituted with one or more, for example one or two, side chain or straight chain C 1 -C 6 alkyl, such as methyl, ethyl, propyl, butyl, pentyl or hexyl, especially C 1 -C 4 alkyl . Examples are dimethylpyridyl, dimethylpyrrolyl or methylfuryl.
    Examples of compounds of formula (VI) include .
    In compounds of formula I and formula III, R 1 is phenyl optionally substituted with one or more C 1 -C 6 alkyl, phenyl, halogen, OR 8 , SR 9 or NR 10 R 11 , the blocks and / or one or more hydroxyl groups as hydroxyl, optionally substituted C 6 -C 20 alkyl or C 2 -C 20 alkyl composition.
    R 1 is preferably one or more C 1 -C 6 alkyl, phenyl, halogen, OR 8, SR 9 or NR 10 R 11, or a substituted or unsubstituted phenyl, one or more C 1 -C 6 alkyl, phenyl, OR 8, with a SR 9 or NR 10 R 11 is optionally substituted C 6 -C 20 alkyl.
    Preference is given to compositions comprising compounds of the formulas I and III, in particular those of formula (I).
    Also, compounds wherein R 3 and R 7 are hydrogen are preferred.
    R 1 is preferably C 1 -C 12 alkyl, especially C 6 -C 12 alkyl.
    R 2 is preferably tolyl, benzoyl or acetyl.
    The oxime esters of formulas I, II, III, IV and V may be prepared by methods described in literature, for example by reacting the corresponding oxime (R 2 ═H) with a base such as a tertiary amine (eg triethylamine) With an acyl chloride or anhydride in an inert solvent such as tetrahydrofuran or dimethylformamide or in a basic solvent such as pyridine.
    In the above scheme, in the case of the compound of formula V, Lt; / RTI > is replaced by a heterocyclic radical.
    Such reactions are well known to those skilled in the art and are generally carried out at a temperature of from -15 to + 50 [deg.] C, preferably from 0 to 20 [deg.] C.
    The compounds of formulas (II) and (IV) Can be similarly obtained using the appropriate oxime of formula (I), wherein R < 7 > and M are as defined above.
    The oxime required as a starting material can be prepared according to standard chemistry textbooks (see J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992) or professional monographs (see SR Snadler and W. Karo, Organic functional group preparations, , Academic Press).
    One of the most common methods is the reaction of a ketone with a hydroxylamine or a salt thereof in a polar solvent such as, for example, ethanol or aqueous ethanol. In this case, a base such as sodium acetate is added to adjust the pH of the reaction mixture. It is well known that the rate of the reaction is pH-dependent and the base can be added continuously at the beginning of the reaction or during the reaction. As the base and / or the solvent or the co-solvent, a basic solvent such as pyridine may be used. The reaction temperature is generally the reflux temperature of the mixture, typically 60 to 120 ° C. Another common oxime synthesis method is the nitration of " active " methylene groups with nitrous acid or alkyl nitrite. Two alkaline conditions as described in the literature (see Organic Syntheses coll Vol. VI, J. Wiley & Sons, New York, 1988) and the literature (see Organic Syntheses coll Vol V, pp32 and 373, coll. III, pp 191 and 513, coll. Vol. II, pp. 202, 204 and 363 are suitable as starting materials for the present invention. Nitrite is typically prepared from sodium nitrite. Alkyl nitrites can be, for example, methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite or isoamyl nitrite. All oxime ester groups can exist in two configurations of (Z) or (E). Isomers can be separated by conventional methods, but isomer mixtures can also be used as photoinitiated species.
    The compounds of formulas I, II, III, IV and V can be used as photoinitiators for photopolymerization of ethylenically unsaturated compounds or mixtures comprising these compounds.
    Component (A) in the composition according to the invention is an oligomer or polymer containing at least one free carboxylic acid group in the molecule.
    Particularly preferred are compositions wherein the oligomer or polymer (A) contains two or more polymerizable ethylenically unsaturated groups.
    Component (A) may exhibit moderate (oligomeric) or high (polymeric) molecular weights. An example of such a component is an oligomer or polymer obtained by reacting a saturated or unsaturated polyfunctional acid anhydride with the reaction product of an epoxy compound with an unsaturated monocarboxylic acid. The epoxy compound used to make the most interesting compositions is novolak type epoxy.
    Said resin, which can be cured by an activating energy beam, can be prepared by reacting the reaction product of a novolac type epoxy compound (hereinafter described) with an unsaturated monocarboxylic acid in the presence of a phthalic anhydride or an aromatic polycarboxylic anhydride such as trimellitic anhydride or pyromellitic acid Lt; / RTI > acid anhydride, such as an anhydride. In such a case, it is proved that a resin in which the amount of the acid anhydride used in the reaction at the time of production exceeds 0.15 mol per hydroxyl group contained in the reaction product of the novolak type epoxy compound and the unsaturated carboxylic acid is particularly suitable.
    The acid value of the resin thus obtained is suitably in the range of 45 to 160 mg KOH / g, preferably 50 to 140 mg KOH / g.
    When the number of ethylenic unsaturated bonds present in the molecular unit of the resin that can be cured by the activation energy ray is small, the photopolymerization proceeds slowly, so that it is preferable to use a novolak type epoxy compound as the raw material. In order to lower the viscosity of the ink, a bisphenol A type epoxy compound can be used instead.
    The novolac-type epoxy compounds represent phenol novolac-type epoxy resins and cresol novolac-type epoxy resins. Compounds prepared by reacting epichlorohydrin with a suitable novolak resin in a conventional manner can be used. Typical examples of the acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyl neomethylenetetrahydro Dicarboxylic anhydrides such as phthalic anhydride, chlorendic anhydride and methyltetrahydrophthalic anhydride; Aromatic polycarboxylic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride and benzophenone-tetracarboxylic acid dianhydride; And a polycarboxylic acid anhydride derivative such as 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride.
    Further examples of the component (A) include an epoxy group-containing acrylic acid ester or a methacrylic acid ester compound obtained by adding an epoxy group-containing acrylic acid ester or methacrylic acid ester compound to a part of a carboxyl group of a copolymer produced by the reaction of an acrylate or methacrylate with acrylic acid or methacrylic acid There are reaction products.
    Copolymers of acrylic acid esters and / or methacrylic acid esters with acrylic acid and / or methacrylic acid may be prepared by reacting one or two or more acrylic acid esters and / or methacrylic acid esters of formulas (1) and (2) Is obtained by copolymerizing acrylic acid and / or methacrylic acid of formula (2).

    In the above formulas (1) and (2)
    R a is a hydrogen atom or a methyl group,
    And R b is an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
    Preferably, the molar ratio of acrylic esters and / or methacrylic esters to acrylic acid and / or methacrylic acid is from 30:70 to 70:30.
    The ester group of each of the acrylic acid esters and / or methacrylic acid esters can be appropriately selected from various aliphatic groups having 1 to 6 carbon atoms.
    The reaction product is obtained by adding an acrylic acid ester and / or a methacrylic acid ester having a terminal epoxy group of the formula (3) to the thus obtained copolymer.
    In the above formula (3)
    R a is as defined above,
    R c is an aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 12 carbon atoms.
    In order to obtain a reaction product suitable for the present invention, the compound of the formula (3) is added to the monomers of the formula (1) and the formula (2) in a proportion of 10 to 40 mol% to obtain a copolymer having an ultraviolet curing ability.
    The reaction product thus obtained preferably has an average molecular weight of 20,000 to 70,000, a softening point of preferably 35 to 130 ° C and an acid value of 50 to 150.
    A further example of component (A) is a resin having an alpha, beta -unsaturated double bond in its side chain and an acid value of 50 to 200. For example, the photopolymerizable resin comprises 70 to 95% by weight of an ethylenically unsaturated acid component and a copolymerizable component thereof. It has a carboxyl value of 500 or more, preferably 600 or more, especially 620 or more, and a number average molecular weight of 1,000 to 100,000, preferably 3,000 to 70,000, in terms of the acid value (here, the acid value represents the number of mg of potassium hydroxide necessary for neutralizing 1 g of the resin) Group-containing resin and an unsaturated compound having an , - unsaturated double bond and an epoxy group. The content of the ethylenically unsaturated acid component in the carboxyl group-containing resin of the photopolymerizable resin is such that the photopolymerizable resin (A) is insoluble in water or a diluted alkaline aqueous solution even after adding an unsaturated compound having an , - unsaturated double bond and an epoxy group And the solubility thereof is maintained, it is 70 to 95% by weight. An example of such a resin is described in JP-A-8-339081.
    The carboxyl group-containing resin (A) is, for example, an ethylenically unsaturated acid monomer in an amount of 70 to 95% by weight, preferably 78 to 88% by weight, particularly 80 to 85% by weight and 5 to 30% by weight, 22 to 12% by weight, in particular 15 to 20% by weight, of copolymerizable monomers in an appropriate unreacted solvent and thermally polymerizing these solutions in the presence of a thermal polymerization initiator at 45 to 120 캜. Therefore, a carboxyl group-containing resin having an acid value of 500 or more and a number average molecular weight of 1,000 to 100,000 can be produced with high safety and high stability.
    Specific examples of the ethylenically unsaturated monomers suitable for preparing the carboxyl group-containing resin (A) include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, angeic acid, thylacetic acid, 2-ethylacrylic acid, 3- Dihydrophthalic acid monohydroxyethyl acrylate, tetrahydrophthalic acid monohydroxyethyl acrylate, hexahydrophthalic acid monohydroxyethyl acrylate, hexahydrophthalic acid monohydroxyethyl acrylate, hexahydrophthalic acid monohydroxyethyl acrylate, hexahydrophthalic acid monohydroxyethyl acrylate, Acrylic acid dimer, acrylic acid trimer, ω-carboxy-polycaprolactone monoacrylate, and ω-carboxy-polycaprolactone monomethacrylate. Of these monomers, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, angeic acid, thylacetic acid, 2-ethylacrylic acid, 3-propylacrylic acid, 3-isopropylacrylic acid, -Carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate and the like are preferable, and acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, angeic acid, thylacetic acid, 2-ethylacrylic acid, 3-propylacrylic acid, 3- , ω-carboxy-polycaprolactone monoacrylate and ω-carboxy-polycaprolactone monomethacrylate are particularly preferred. These monomers may be used alone or in admixture of two or more.
    Suitable copolymerizable monomers are acrylic acid esters, methacrylic acid esters, vinyl monomers, styrene type monomers and cyclic ester monomers. Specific examples thereof include 2-hydroxymethyl acrylate, 2-hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2- Ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, dipentaerythritol hexaacrylate, Acrylic acid amide, methacrylic acid amide, methacrylic acid amide, methacrylic acid amide, methacrylic acid amide, dimethylacrylamide, , Arc Acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl Acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, acrylic acid carbitol, methacrylic acid carbitol, -Caprolactone-modified tetrafurfuryl acrylate, -Caprolactone-modified Acrylonitrile, acrylonitrile, methacrylonitrile, methacrylonitrile, methacrylonitrile, methacrylonitrile, methacrylonitrile, methacrylonitrile, methacrylonitrile, , Tridecyl methacrylate, stearyl acrylate, stearyl methacrylate, and the like The. These monomers may be used alone or in admixture of two or more.
    Suitable thermal polymerization initiators include, for example, 2,2'-azobis- (2,4-dimethylvaleronitrile) (available temperature 45 to 70 ° C), 2,2'-azobis (isobutyronitrile (Available temperature 60 to 90 占 폚), 2,2'-azobis (2-methylisobutyronitrile) (available temperature 60 to 95 占 폚), tertiary butyl peroctoate Azobis (cyclohexane-1-carbonitrile) (available temperature 80 to 110 ° C) or 1 - [(1-diazo-1-methylethyl) azo] -formamide Possible temperature 95 to 120 占 폚). One or more of the above compounds are used.
    Thereafter, the carboxyl group-containing resin produced according to the above-mentioned method is esterified by esterification using an unsaturated compound having an , - unsaturated double bond and an epoxy group to esterify the carboxyl group and form an , - unsaturated double bond ≪ / RTI > Examples of suitable compounds having an alpha, beta-unsaturated double bond and an epoxy group are given below. At least one component selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, compounds of formulas (4), (5) and (6) as defined below is used.

    In the above formulas 4 to 6,
    R < 1 > is hydrogen or methyl,
    n 'is an integer of 1 to 10,
    R 2 'is hydrogen or methyl,
    n " is an integer of 1 to 3;
    Of these compounds, a compound having an alicyclic epoxy group is particularly preferable because such a compound is highly reactive with a carboxyl group-containing resin and can shorten the reaction time. In addition, these compounds do not cause gelation during the reaction process and allow the reaction to be carried out stably. On the other hand, glycidyl acrylate and glycidyl methacrylate are advantageous in terms of sensitivity and heat resistance since they have a small molecular weight and can exhibit high ester conversion.
    The photopolymerizable resin obtained by the above-mentioned method has an , - unsaturated double bond on the side chain. Its acid number is from 50 to 200, preferably from 70 to 150, in particular from 85 to 120. The number average molecular weight thereof is 7,000 to 10,000, and the phase transition point (hereinafter referred to as Tg) is 30 to 120 ° C. When a photopolymerizable resin is used as the solder resist, the acid value thereof is preferably 70 or more, because other additive components can be added to the composition.
    When the esterification is carried out and the photosensitive resin composition is produced, an inert organic solvent is used.
    Examples of commercially available unsaturated compounds (A) as described above include EB3800, EB9692, EB9694, EB9695, EB9696 (UCB Chemicals), KAYARAD TCR1025 (Nippon Kayaku Co., LTD), NEOPOL 8319 Pica), EA-6340 (manufactured by Shin Nakamura Chemical Co., Ltd.), ACA 200M, ACA 250 (manufactured by Daicel Industries, Ltd.).
    It is preferable that the oligomer or polymer (A) is a resin obtained by reacting a saturated or unsaturated polyfunctional acid anhydride with the reaction product of an epoxy compound and an unsaturated monocarboxylic acid, or between the unsaturated compound having an , - unsaturated double bond and an epoxy group and a carboxyl group- Compositions which are formed adducts are preferred.
    Examples of suitable reactive or non-reactive diluents (C) for compositions according to the invention are photopolymerizable vinyl type monomers and / or organic solvents. Representative examples of photopolymerizable vinyl type monomers include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate and the like; Mono- or di-acrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol and the like; Acrylamide such as N, N-dimethyl acrylamide, N-methylol acrylamide and the like; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate; Polyhydric acrylates of polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate and the like or their ethylene oxide or propylene oxide adducts; Acrylates of phenoxy acrylates, bisphenol A diacrylates, and ethylene oxide or propylene oxide adducts of these phenols; Acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylol propane triglycidyl ether, triglycidyl isocyanurate and the like; And melamine acrylate and / or methacrylate corresponding to the above acrylate.
    On the other hand, examples of suitable organic solvents include ketones such as ethyl methyl ketone, cyclohexanone and the like; Aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene and the like; Methyl cellosolve, ethyl cellosolve, butyl cellosolve, benzyl cellosolve, phenyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, triethylene Glycol ethers such as glycol monoethyl ether and the like; Esters such as ethyl acetate, butyl acetate, and esterified products of the glycol ethers described above (e.g., cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate); Alcohols such as ethanol, propanol, n-butanol, n-hexanol, n-heptanol, n-octanol, ethylene glycol, propylene glycol and the like; Aliphatic hydrocarbons such as octane, decane and the like; Petroleum ether solvents, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. The organic solvent is used to dilute the resin so that it can be easily coated.
    The diluent (C) as described above may be used alone or in combination of two or more. A suitable amount is 5 to 300 parts by weight, preferably 10 to 150 parts by weight, based on 100 parts by weight of component (A).
    The diluent is used to dilute the components of the mixture so that they can be easily coated. Another object is to enhance photopolymerization when a photopolymerizable vinyl type monomer is used. In addition, when an organic solvent is used as a diluent, the diluent may help to dissolve and dilute the photosensitive prepolymer so that the prepolymer may be diluted to a liquid state and dried to form a film. Thus, depending on the diluent used, either a contact system in which the photomask is in contact with the coating film or a non-contact system (e.g. laser beam recording) may be used.
    Preferably, component (C) is a monomer having two or more acrylate or methacrylate groups.
    As the thermosetting component (D), a compound having an epoxy group is used. Known liquid or solid epoxy compounds can be used, and these epoxy compounds are used according to the required properties. For example, a liquid epoxy resin is used when it is desired to improve the resistance to electrolysis, and an epoxy resin having a plurality of methyl groups in a benzene ring or a cycloalkyl ring is used when water resistance is required. Preferred examples of the epoxy resin include bisphenol S such as BPS-2000 (manufactured by Nippon Kayaku Co., Ltd.), EPX-30 (manufactured by ACR Co.), Epicuron EXA-1514 (manufactured by Dainippon Ink & Chemicals Inc.) Type epoxy resin; Bisphenol A type epoxy resins such as Epicuron N-3050, N-7050, N-9050 (manufactured by Dainippon Ink & Chemicals Inc.), XAC-5005, GT-7004, 6484T, 6099 Suzy; Bisphenol F type epoxy resin such as YDF-2004, YDF 2007 (manufactured by Tohto Kasei Co.); Diglycidyl phthalate resins such as Blemmer DGT (manufactured by Nippon Oil and Fats Co. Ltd.); A heterocyclic epoxy resin such as TEPIC (manufactured by Nissan Chemical Industries, Ltd.), Araldite PT810 (manufactured by Ciba Specialty Chemicals Inc.); A biscylenol type epoxy resin such as YX-4000 (manufactured by Yuka Shell Co.); Biphenol type epoxy resin such as YL-6056 (manufactured by Yuka Shell Co.); Tetraglycidyl xylylenoyl ethane resins such as ZX-1063 (Tohto Kasei Co.) and the like; ECN-292 and ECN-299 (manufactured by Asahi Chemical Industry Co., Ltd .; Nippon Kayaku Co., Ltd.), EPN- YDCN-220HH, YDCN-702, YDCN-704, YDPN-601 and YDPN-602 (manufactured by Ciba Specialty Chemicals Inc.). Novolac type epoxy resins such as Tohto Kasei Co., Epicuron-673, N-680, N-695, N-770 and N-775 (manufactured by Dainippon Ink & Chemicals Inc.); Novolacs of bisphenol A such as EPX-8001, EPX-8002, EPPX-8060 and EPPX-8061 from Asahi Chemical Industry Co., Ltd., Epicuron N-880 from Dainippon Ink & Type epoxy resin; Chelate-type epoxy resins such as EPX-49-69 and EPX-49-30 (Asahi Denka Kogyo K.K.); A glyoxal-type epoxy resin such as YDG-414 (manufactured by Tohto Kasei Co.); Amino group-containing epoxy resins such as YH-1402 and ST-110 (manufactured by Tohto Kasei Co.), YL-931 and YL-933 (manufactured by Yuka Shell Co.) Rubber-modified epoxy resins such as Epicuron TSR-601 (Dainippon Ink & Chemicals Inc.), EPX-84-2 and EPX-4061 (Asahi Denka Kogyo K.K.); Dicyclopentadiene phenol type epoxy resin such as DCE-400 (manufactured by Sanyo-Kukusaku Pulp Co., Ltd.); Silicone modified epoxy resins such as X-1359 (manufactured by Asahi Denka Kogyo K.K.); Caprolactone modified epoxy resins such as Plaque G-402 and G-710 (manufactured by Dicel Chemical Industries, Ltd.), and the like. Further, compounds obtained by partially esterifying these epoxy compounds (for example, esterified with (meth) acrylate) may be used in combination.
    An appropriate amount of the component (D) used in accordance with the present invention is 10 to 150 parts by weight, preferably 20 to 80 parts by weight, based on 100 parts by weight of the component (A).
    Preferably, component (D) is bisphenol A, bisphenol S, bisphenol F or novolac type epoxy compounds.
    In some cases, it may be advantageous to use the photosensitizer compound with the compounds of formulas I, II, III, IV, V and VI. It is therefore a further object of the present invention to further comprise one or more photosensitizer compounds (E) and / or additional additives (F) in addition to component (A), component (B), component (C) ≪ / RTI >
    Photopolymerization can be promoted by additionally adding a photosensitizer compound (E) that moves or broadens the spectral sensitivity. Such compounds include, in particular, aromatic carbonyl compounds such as benzophenone, thioxanthone, anthraquinone and coumarin derivatives such as 3-acyl coumarin, 3- (aroylmethylene) thiazoline, camphorquinone But also eosin, rhodamine and erythrosine dyes, as well as all compounds which can be used as auxiliary initiators as described above.
    Further suitable examples of such photosensitizers are:
    1. Thioxanthone
    Thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1- 2-ethoxycarbonylthioxanthone, 3- (2-methoxyethoxycarbonyl) thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methylthio 1-ethoxycarbonyl-3-chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxycortic acid, 2-ethoxycarbonyl-3 3-phenylsulfurylthioxanthone, 3,4-di- [2- (2-methoxyethoxy) ethoxycarbonyl] thioxanthone, 1-ethoxycarbonyl- 3- (1-methyl-1-morpholinoethyl) thioxanthone. Methyl-6- (1,1-dimethoxybenzyl) thioxanthone, 2-morpholinomethylthioxanthone, 2-methyl-6-morpholinomethylthioxanthone, 2- N-octylthioxanthone-3, 4-dicarboximide, N- (1,1,3,3-tetramethyl Butyloxycarbonyl-2-methylthioxanthone, 6-ethoxycarbonyl-2-methyloxoctanoate, 6-ethoxycarbonyl-2-methylthioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy) -N, N, N-trimethyl- Propanammonium chloride;
    2. Benzophenone
    Benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'dimethylamino Benzophenone, 4,4'-diethylaminobenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4- (4-methylthiophenyl) benzophenone, 3,3'- Benzoyl-N, N, N-trimethylbenzene, 4- (2-hydroxyethylthio) benzophenone, 4- N, N, N-trimethyl-1-propanaminium chloride monohydrate, 4- (13-acryloyl- Benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyl) oxy] ethyl-benzenemethanaminium chloride;
    3. Coumarin
    Benzoyl-7-methoxyquimarine, 3-benzoyl-5,7-di (propoxy) coumarin, 3-benzoyl-6 , 3,3'-carbonyl-bis [5,7-di (propoxy) coumarin], 3,3'-carbonyl- Methoxycoumarin), 3,3'-carbonyl-bis (7-diethylamino-coumarin), 3-isobutyrylcoumarin, 3-benzoyl-5,7-dimethoxy-coumarin, Benzoyl-5,7-dibutoxy-coumarin, 3-benzoyl-5,7-di (methoxyethoxy) coumarin, 3-benzoyl- ) 3-benzoyl-7-dimethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-isobutyryl- 3-thienoylcoumarin, 3- (4-cyanobenzoyl) -2,3-dihydro- ) -5,7-dimethoxycoumarine .;
    4. 3- (Aroylmethylene) -thiazoline
    3-methyl-2-benzoylmethylene- beta -naphthothiazoline, 3-methyl-2-benzoylmethylene-benzothiazoline, 3-methyl-2-propionylmethylene- beta -naphthothiazoline;
    5. Other carbonyl compounds
    3-methoxyacetophenone, 4-phenylacetophenone, benzyl, 2-acetylnaphthalene, 2-naphthaldehyde, 9,10-anthraquinone, 9-fluorenone, dibenzosuberone, xanthone, 2 (5-bis (4-diethylaminobenzylidene) cyclopentanone, - (para-dimethylaminobenzylidene) ketone such as 2- (4-dimethylaminobenzylidene) N-methyl-3, 5-di (ethylthio) phthalimide, N- (3-methylthiophenyl) Methyl-3,5-di (ethylthio) phthalimide.
    Component (E) is used in an amount of 0.015 to 60 parts by weight, preferably 0.03 to 30 parts by weight, based on 100 parts by weight of component (A).
    The photopolymerizable mixture may contain various additives (F) as well as photoinitiators and / or photosensitizer compounds.
    Examples thereof include thermal inhibitors for preventing early polymerization, for example, hydroquinone, hydroquinone derivatives, p-methoxyphenol, -Naphthol or sterically hindered phenols (e.g., 2,6- Butyl-p-cresol). In order to increase the storage stability in the dark, for example, copper compounds such as copper naphthalate, stearate or octoate, triphenylphosphine, tributylphosphine, triethylphosphite, triphenylphosphite or tri Phosphorus compounds such as benzyl phosphite, quaternary ammonium compounds such as tetramethylammonium chloride or trimethylbenzylammonium chloride, or hydroxylamine derivatives such as N-diethylhydroxylamine. To eliminate atmospheric oxygen during the polymerization reaction, paraffin or similar wax-like components may be added which, due to improper solubility in the polymer, will migrate to the surface at the beginning of the polymerization reaction and form a clear surface layer to prevent the entry of air. An oxygen-impermeable layer may also be used. Photostabilizers that can be added in minor amounts include UV absorbers such as hydroxyphenylbenzotriazole, hydroxyphenylbenzophenone, oxalamide or hydroxyphenyl-s-triazine type UV absorbers. These compounds can be used alone or in admixture with or without sterically hindered amines (HALS)
    Examples of such UV absorbers and photostabilizers are:
    1. 2- (2'-hydroxyphenyl) benzotriazole, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'- (1, 2'-tert-butylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- Butyl-2'-hydroxy-5'-methyl-phenyl) -5-chlorobenzotriazole, 2- (3'- ) Benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3 ', 5'- 2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (3'-tert-butyl-5 '- [2- (2-ethyl-hexyloxy) carbonylethyl] -2 '-Hydroxyphenyl ) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2- methoxycarbonylethyl) 3'-tert-butyl-2'-hydroxy-5'- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'- Benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (3'- -Isobutyloxycarbonylethyl) phenylbenzotriazole, a mixture of 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol- ], An ester exchange reaction product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'- hydroxy- phenyl] benzotriazole with polyethylene glycol 300, [R- CH 2 CH 2 -COO (CH 2 ) 3] 2 - ( wherein, R represents 3'-tert-butyl-4'-hydroxy -5'-2H- benzotriazol 2-yl-phenyl);
    2. 2-hydroxybenzophenones such as 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy- , 4,2 ', 4'-trihydroxy- and 2'-hydroxy-4,4'-dimethoxy derivatives;
    3. Esters of substituted or unsubstituted benzoic acids, for example, tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4- Benzoyl resorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl- Butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate and 2-methyl- Tert-butyl-4-hydroxybenzoate;
    4. Acrylates such as isooctyl or ethyl -Cyano- , -Diphenylacrylate, methyl- -Carbomethoxycinnamate, butyl or methyl -Cyano- Methoxycinnamate, methyl [alpha] -carboxymethoxy-p-methoxy cinnamate and N- ([beta] -carbomethoxy- [beta] -cyanovinyl) -2-methylindoline;
    5. Sterically hindered amines such as bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (2,2,6,6-tetramethylpiperidyl) succinate, bis Bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, bis (1,2,2,6,6-pentamethylpiperidyl) -n-butyl- 4-hydroxybenzylmalonate, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, N, N'-bis- (2 , 2,6,6-tetramethyl-4-piperidyl) hexa-methylenediamine and 4-3-octylamino-2,6-dichloro-1,3,5-s-triazine, (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetra Methylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis- (1,2,2,6,6-pentamethylpiperazine, 2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl- , 3,8-triazaspiro [4.5] decane-2,4-dione, bis- (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis- Oxy-2,2,6,6-tetramethylpiperidyl) succinate, N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4- Dichloro-1,3,5-triazine, a condensation product of 2-chloro-4,6-di- (4-n-butylamino-2,2,6,6-tetramethyl (2-chloro-4,6-di- (4-n-butylamino-1-piperidyl) -1,3,5-triazine and 1,2- , 2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis- (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl Tetramethyl-1,3,8-triazaspiro [4.5] decan-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl Piperidyl) pyrrolidine-2,5-dione and 3 -Dodecyl-l- (1,2,2,6,6-penta-methyl-4-piperidyl) pyrrolidin-2,5-dione;
    6. Oxalamide, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di Di-tert-butyloxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis - (3-dimethylaminopropyl) oxanylamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and 2-ethoxy- Mixtures of o-and p-methoxy- and o- and p-ethoxy-disubstituted oxanilides; mixtures of o- and p-methoxy-disubstituted oxanilides;
    7. 2- (2-hydroxyphenyl) -1,3,5-triazine, for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) Dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) Triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) Phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy- Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-dodecyl / (2-hydroxypropyl) oxy-2-hydroxy-phenyl] -4,6-bis (2,4-dimethylphenyl) ) -1,3,5-triazine;
    8. Phosphites and phosphonites such as triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis- (2,4-di-tert-butylphenyl) phosphite, bis Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythrityl diphosphite, bis-isodecyloxypentaerythrityl diphosphite, bis- 4-di-tert-butyl-6-methylphenyl) pentaerythrityl diphosphite, bis- (2,4,6-tri-tertiary butylphenyl) pentaerythritol diphosphite, triorearyl sorbitol triphosphite , Tetrakis- (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,1 Di-benzo [d, g] -1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12 (2,4-di-tert-butyl-6-methylphenyl) methylphosphite and bis (2,4-di Tert-butyl-6-methylphenyl) ethyl phosphite.
    Additional additives known in the art may be added as component (F), for example, as an anti-static agent, flow improver, adhesion promoter, thickener, defoamer, flow modifier and antistatic agent.
    In order to improve properties such as adhesiveness and hardness in the photosensitive thermosetting resin composition of the present invention, it is possible to use a photosensitive resin composition containing barium sulfate, barium titanate, silicon oxide powder, silicon oxide fine particles, amorphous silica, talc, clay, Inorganic fillers such as calcium carbonate, aluminum oxide, aluminum hydroxide, mica powder and the like can be used. The proportion of the filler in the composition is 0 to 60% by weight, preferably 5 to 40% by weight of the photosensitive thermosetting resin composition.
    If necessary, known additives such as a colorant such as phthalocyanine blue, phthalocyanine green, diazo yellow, crystal biotite, titanium oxide, carbon black, naphthalene black and the like can be used.
    The composition optionally further comprises, as component (F), an epoxy curing accelerator such as, for example, an amine compound, an imidazole compound, a carboxylic acid, a phenol, a quaternary ammonium salt or a methylol group containing compound. The amount of the curing agent used is 0 to 10% by weight, preferably 0.05 to 5% by weight, of the photosensitive thermosetting composition.
    Therefore, the object of the present invention is the above-mentioned composition comprising an additional additive (F) selected from the group consisting of an inorganic filler, a colorant, an epoxy curing agent, a thermal polymerization inhibitor, a thickener, a defoaming agent and an antistatic agent,
    In order to promote photopolymerization, amines such as triethanolamine, N-methyldiethanolamine, p-dimethylaminobenzoate or Michler's ketone can be added. The action of the amine can be enhanced by the addition of aromatic ketones of the benzophenone type. An example of an amine which can be used as an oxygen scavenger is a substituted N, N-dialkyl aniline as described in EP 339841. Other promoters, auxiliary initiators and autooxidants include, for example, thiols, thioethers, disulfides, phosphonium salts such as those described in EP 438123, GB 2180358 and JP 6-68309 , Phosphine oxide or phosphine.
    Chain transfer agents customary in the art may be added to compositions according to the present invention. Examples are mercaptans, amines and benzothiazoles.
    The curing process can be carried out in particular by means of a composition colored with (for example, titanium dioxide) or under a heating condition, a component which forms a free radical, for example 2,2'-azobis (4-methoxy- -Dimethylvaleronitrile), triazenes, diazosulfides, azo compounds such as pentaazadiene or hydroperoxides or peroxycarbonates (for example t-butyl hydroperoxide as described in EP 245639) and Can be promoted by adding the same peroxy compound.
    The composition according to the invention may also contain as a further additive (F) a photo-reducible dye, for example xanthene, benzoxanthene, benzothioxanthene, thiazine, pyrionine, porphyrin or acridine Dyes and / or trihalomethylmethyl compounds which can be decomposed by irradiation. A similar composition is described, for example, in EP 4,456,224.
    Depending on the intended use, further customary additives (F) are optical brighteners, wetting agents or antistatic agents.
    In order to cure the thick film, for example, it is suitable to add glass microspheres or ground glass fibers as described in U.S. Patent No. 5,013,768.
    The additive (s) (F) are selected according to the application field and the properties required for such field. The additives described above are conventional in the art and are therefore added in amounts that are useful for their respective uses.
    In certain cases, it may be advantageous to use a mixture of two or more o-acyloxime photoinitiators. Of course, a mixture with known photoinitiator (B1), for example, camphorquinone, benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives such as -Hydroxycycloalkylphenylketone or 2-hydroxy Methyl-1-phenyl-propane, dialkoxyacetophenone, -Hydroxy- or -Amino-acetophenone, such as (4-methylthiobenzoyl) Ethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 4-aroyl-1,3-dioxolane, benzoin alkyl ethers and benzyl ketals such as dimethylbenzyl ketal, phenyl (2,4,6-trimethylbenzoyl) -diphenylphosphine oxide, bisacylphosphine oxide, bis (2, 3, 4-trimethylbenzoyl) , 6-dimethoxy-benzoyl) - (2,4,4-trimethylpentyl) phosphine oxide, bis (2,4,6-trimethyl Bis (2,4,6-trimethylbenzoyl) -2,4-dipentoxyphenylphosphine oxide, trisacylphosphine oxide, ferrocene compound or titanocene, such as bis (cyclopenta Dienyl) -bis (2,6-difluoro-3-pyrylphenyl) titanium can also be used.
    When o-acyloxime photoinitiators are used in hybrid systems, in addition to free radical curing agents, cationic photoinitiators such as peroxide compounds such as benzoyl peroxide (other suitable peroxides are described in U.S. Patent Nos. 4950581, 19 Columns 17 to 25), aromatic sulfonium, phosphonium or iodonium salts as described in U.S. Patent No. 4950581, column 18, line 60 to column 19, line 10, or cyclopentadienyl-arene (II) complex salt [for example, (η 6 -isopropylbenzene) (η 5 -cyclopentadienyl) iron (II) hexafluorophosphate] as well as EP 780729 Oxime sulfonic acid esters as described can be used.
    Accordingly, the object of the present invention is a composition further comprising at least one photoinitiator (B1).
    The photoinitiator (B) is usually added in an amount of 0.015 to 60 parts by weight, preferably 0.03 to 30 parts by weight, based on 100 parts by weight of the component (A).
    The amount represents the sum of all the photoinitiators added if a mixture of initiators is used. Therefore, the amount represents the photoinitiator (B) or the photoinitiator (B) + (B1).
    The present invention also relates to a composition comprising 100 parts by weight of component (A), 0.015 to 60 parts by weight of component (B), 5 to 300 parts by weight of component (C), 10 to 150 parts by weight of component (D) ≪ / RTI >
    It has been found that a novel radiation sensitive composition which can be developed without being swollen in an aqueous alkali medium is very sensitive to light and can be used as a negative type resist. They are suitable as photosensitive resists (electroless plating resists, electroplating resists, etching resists, solder resists) in the field of electronics.
    The composition is applied uniformly to the substrate by spin coating, dip coating, knife coating, curtain coating, screen coating, brushing, spraying, especially electrostatic spraying and reverse roll coating, or electrophoretic painting. In addition, the photosensitivity is applied to a temporary flexible substrate and then the layer is transferred by lamination to a final substrate, for example, a copper-coated circuit board.
    The amount applied (film thickness) and the properties of the substrate (layer support) depend on the intended application field. The film thickness range is generally about 0.1 to 100 μm or more, for example, 0.1 to 1 cm, preferably 1 to 1000 μm.
    After coating the substrate, the solvent is generally removed by drying to leave a film of the photoresist on the substrate.
    The object of the present invention is also a solder corrosion resistant film comprising the composition as described above.
    The term " image " exposure refers to the exposure of a photomask including a pattern, for example, a slide or a laser or beam of light, which moves, for example, onto a substrate coated under computer control, And exposure by irradiation with a computer-controlled electron beam. As described in A. Bertsch, JY Jezequel, JC Andre in Journal of Photochemistry and Photobiology A: CHemistry 1997, 107, p. 275-281 and KP Nicolay in Offset Printing 1997, 6, A digital image can be made using a mask made of a liquid crystal capable of addressing pixels together.
    As noted above, the composition can be developed with an aqueous alkali. Particularly suitable aqueous alkaline developers are aqueous solutions of tetraalkylammonium hydroxides or alkyl metal silicates, phosphates, hydroxides and carbonates. If desired, a small amount of wetting agent and / or organic solvent may be added to these solutions. Examples of common organic solvents that can be added in small amounts to developers include cyclohexanone, 2-ethoxyethanol, toluene, acetone, and mixtures of these solvents.
    The sensitizing sensitivity of the novel compositions can generally be extended from about 200 nm to 600 nm (UV-visible region). Suitable radiation is, for example, in sunlight or in light rays from an artificial light source. Thus, a large number of different types of light sources are used. Point sources and arrays ("lamp carpets") are suitable. Examples thereof include carbon arc lamps which may include metal halide dopes, xenon arc lamps, medium pressure, high pressure and low pressure mercury lamps (metal-halogen lamps), microwave-stimulated metal vapor lamps, excimer lamps, Fluorescent lamps, argon incandescent lamps, electronic flash lamps, photographic floodlights, light emitting diodes (LED), electron beams and X-rays. The distance between the substrate and the lamp exposed in accordance with the present invention may vary depending on the intended use and the type and power of the lamp and may be, for example, 2 to 150 cm. Excimer lasers, such as a Krypton F laser for exposure at 248 nm, may also be suitable. A laser in the visible light region may also be used. By this method, it is possible to manufacture printed circuits, offset printing plates for lithographs or relief printing plates and photo image recording materials in the electronic industry.
    Accordingly, the present invention includes the application of a photoinitiator of one or more of formulas I, II, III, IV, V or VI as described above to said compound to produce a composition which is then irradiated with a beam of electromagnetic radiation, in particular at a wavelength of 190 to 600 nm A method of photopolymerizing a compound containing at least one ethylenically unsaturated double bond, which comprises the step of irradiating a composition as described above with electromagnetic radiation, electron beams or X-rays in the range of 190 to 600 nm, To provide a photopolymerization method of the compound.
    The present invention also includes a method for photographically producing a relief image by exposing a coated substrate to a coated substrate having at least one surface coated with the above composition, and removing the unexposed portion with a solvent.
    (1) mixing the components of the above composition, (2) applying the resulting composition to the substrate (coating the substrate), (3) evaporating the solvent present, for example, at a temperature of from 80 to 90 & (4) exposing the coated substrate to radiation through a negative mask (through which the reaction of the acrylate is initiated), (5) developing the irradiated sample by washing with an alkaline aqueous solution to remove the uncured region, and 6) A method of thermally curing a sample, for example, at a temperature of about 150 캜 to initiate crosslinking between a carboxylic acid and an epoxy component to form an image, for example, a method for producing a solder mask The use of the compositions according to the invention in particular is particularly preferred.
    Such a method is another object of the present invention.
    The compositions of the present invention are suitable for use in photosensitive resist compositions which have high sensitivity and resolution, especially in the presence of a photosensitizer or in the presence of a photosensitizer. They have excellent thermal stability and low volatility. '
    The following examples illustrate the invention in more detail. Parts and percentages in the specification and claims are by weight unless otherwise stated. In the absence of reference to a particular isomer in an alkyl radical having one or more carbon atoms, it is meant in each case an n-isomer.
    The following oxime ester photoinitiators are used in the examples.
    The following photosensitizers are used in the examples:
    Michiru Ketone
    Quantacure ITX
    Example 1
    Two photocurable formulations for photosensitivity testing are prepared by mixing the following components.
    A. 200 parts by weight of an acrylated acrylic copolymer (ACA 200M, Daicel Industries, Ltd.), 15.0 parts by weight of dipentaerythritol hexaacrylate (DPHA) (manufactured by UCB Chemicals), phenol novolac epoxy (GY1180; 45.0 parts by weight of Ciba Specialty Chemicals) and 3.2 parts by weight of a photoinitiator;
    B. 153.0 parts by weight of tris-phenol methane epoxy acrylate (TCR1025, manufactured by Nippon Kayaku Co., Ltd.) modified with an acid anhydride, 15.0 parts by weight of dipentaerythritol hexaacrylate (DPHA) 45.0 parts by weight of phenol novolak epoxy (GY1180, manufactured by Ciba Specialty Chemicals) and 3.2 parts by weight of a photoinitiator;
    C. 142.9 parts by weight of novolak epoxy acrylate modified with an acid anhydride (NEOPOL8319, U-Pica), 15.0 parts by weight of dipentaerythritol hexaacrylate (DPHA) (UCB Chemicals), 15 parts by weight of phenol novolac epoxy 45.0 parts by weight of GY1180, manufactured by Ciba Specialty Chemicals) and 3.2 parts by weight of a photoinitiator.
    All operations are carried out under a yellow light. The formulation is applied to an aluminum plate. The solvent is removed by heating in a convection oven at 80 DEG C for 15 minutes. The dry film had a thickness of 25 mu m. An acetate film is applied to this coating, and a standardized test negative having 21 steps with different optical densities is placed thereon (a stepper step wedge). The sample is covered with a second UV-permeable film and compressed into a metal plate by vacuum. Using a 3 kW metal halide lamp (ORC, model SMX 3000) at a distance of 60 cm, the first test is exposed for 40 seconds, the second test is for 80 seconds, and the third test is for 160 seconds. After the exposure, the cover film and the mask are removed, and the exposed film is developed with a 1% sodium carbonate aqueous solution at 30 캜 for 180 seconds using a spray developing machine (Walter Lemmen, model T21). The photosensitivity of the initiator system used is ascertained by the number of steps remaining at the highest number that remains (i.e., polymerized) after development. The greater the number of steps, the greater the sensitivity of the test system.
    To the above formulation, 0.32 part by weight of a mixture of 2-isopropylthioxanthone and 4-isopropylthioxanthone (product name: Quantacure ITX, International Biosynthetics) or 0.07 part by weight of non-flowing ketone was added, , And further tests are carried out. The results are summarized in Tables 1 and 2.
    Photosensitivity results of Composition A PhotoinitiatorPhotosensitive agentNumber of steps reproduced after exposure time 40 seconds80 seconds160 seconds One 6811 OneQuanTacure ITX81114 OneMilk ketone71013 3QuanTacure ITX91114 3Milk ketone7912 6QuanTacure ITX81013 7-6811 7QuanTacure ITX81114 7Milk ketone71013
    Photosensitivity of composition B PhotoinitiatorPhotosensitive agentNumber of steps reproduced after exposure time 40 seconds80 seconds160 seconds One 6810 OneQuanTacure ITX91113 3QuanTacure ITX101214 5QuanTacure ITX91113
    Photosensitivity of Composition C PhotoinitiatorPhotosensitive agentNumber of steps reproduced after exposure time 40 seconds80 seconds160 seconds OneQuanTacure ITX71012 3QuanTacure ITX101214 3Michiru Ketone7912 5QuanTacure ITX91113 6QuanTacure ITX91113 6Milk ketone6911 7QuanTacure ITX81012
    Example 2
    Photocurable formulations for the development test were prepared by dissolving 153.0 parts by weight of tris-phenol methane epoxy acrylate (TCR1025, Nippon Kayaku Co., Ltd.) modified with acid anhydride, dipentaerythritol hexaacrylate (DPHA) 15.0 weight parts of phenol novolac epoxy (GY1180, manufactured by Ciba Specialty Chemicals) and 15.0 weight parts of photoinitiator compound (compounds 1, 2, 3, 4, 5, 6, 7) do.
    All operations are carried out under a yellow light. The formulation is applied to an aluminum plate. The dry film had a thickness of 25 mu m. The coating is heated at 100 占 폚 for 40 minutes, 50 minutes or 60 minutes. After the heat treatment, the film is developed with a 1% sodium carbonate aqueous solution at 30 DEG C for 180 seconds using a spray developing machine (Walter Lemmen, model T21).
    When all of the test oxime photoinitiator compounds, i. E. The compounds of formulas 1 to 7, are used, the composition is fully developable and no undeveloped residues remain.
    权利要求:
    Claims (12)
    [1" claim-type="Currently amended] (A) an oligomer or polymer (A) containing at least one carboxylic acid group in the molecule, at least one compound (B) of formula I, II, III, IV, V or VI, a photopolymerizable reactive or nonreactive diluent (D) as a thermosetting component containing at least two epoxy groups in the thermosetting liquid composition.
    Formula I

    (II)

    (III)

    Formula IV

    Formula V

    VI

    In the above formulas I to VI,
    R 1 is phenyl optionally substituted with one or more C 1 -C 6 alkyl, phenyl, halogen, OR 8 , SR 9 or NR 10 R 11 ; C 2 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, or C 2 -C 20 alkyl optionally interrupted with one or more -O- and / or optionally substituted with one or more hydroxyl groups ; C 2 -C 20 alkanoyl or benzoyl, which is unsubstituted or substituted by one or more C 1 -C 6 alkyl, phenyl, OR 8 , SR 9 or NR 10 R 11 ; C 2 -C 12 alkoxycarbonyl wherein at least one -O- is optionally interrupted and / or optionally substituted with one or more hydroxyl groups; Phenoxycarbonyl optionally substituted by C 1 -C 6 alkyl, halogen, phenyl, OR 8 or NR 10 R 11 ; Or S (O) m - wherein R is unsubstituted or substituted by C 1 -C 12 alkyl, -CONR 10 R 11 , CN, NO 2 , C 1 -C 4 haloalkyl, S (O) m C 1 -C 6 alkyl, C 6 -C 12 aryl, SO 2 OC 1 -C 6 alkyl, SO 2 OC 6 -C 10 aryl or diphenyl-phosphinoyl,
    R 1 together with R 3 or R 1 together with R 7 may form a 5 or 6 membered ring having one or more CO- and / or oxime groups,
    m is 1 or 2,
    R 2 is C 2 -C 12 alkanoyl optionally substituted by one or more halogens or CN; C 3 -C 12 alkenoyl or benzoyl which is unsubstituted or substituted by one or more C 1 -C 6 alkyl, phenyl, halogen, CN, OR 8 , SR 9 or NR 10 R 11, which is a substituent; C 1 -C 6 alkyl or C 2 -C 12 alkoxycarbonyl or phenoxycarbonyl which is unsubstituted or substituted by halogen,
    R 3 , R 4 , R 5 , R 6 and R 7 are each independently hydrogen, halogen, C 1 -C 12 alkyl, cyclopentyl, cyclohexyl or substituted with one or more OR 8 , SR 9 or NR 10 R 11 Unsubstituted phenyl; Benzyl, benzoyl, C 2 -C 12 alkanoyl, C 2 -C 12 alkoxycarbonyl, optionally substituted with one or more -O-, and / or optionally substituted with one or more hydroxyl groups; Phenoxy carbonyl group or OR 8, SR 9, SOR 9 , SO 2 R 9, NO 2, CN, CONR 10 R 11 or NR 10 R 11 group (wherein the substituents OR 8, SR 9 and NR 10 R 11 is phenyl With the additional substituents present on the ring or with one of the carbon atoms of the phenyl ring to form a 5 or 6 membered ring via the radicals R 8 , R 9 , R 10 and / or R 11 ,
    R 8 is hydrogen, C 1 -C 12 alkyl, or -OH, -SH, -CN, C 1 -C 4 alkoxy, C 3 -C 6 alkenoxy, -OCH 2 CH 2 CN, -OCH 2 CH 2 C 2 -C 6 alkyl substituted with COO (C 1 -C 4 alkyl), -OCO-C 1 -C 4 alkyl, -OCO-phenyl, COOH or COO (C 1 -C 4 alkyl); C 2 -C 6 alkyl substituted with one or more -O-; Halogen, C 1 -C 12 alkyl or C 1 -C 4 alkoxy which is unsubstituted or substituted by - (CH 2 CH 2 O) n H, C 2 -C 8 alkanoyl, C 2 -C 12 alkenyl, C 3 -C 6 alkanoyl alkenyl, cyclohexyl or phenyl; Phenyl-C 1 -C 3 alkyl or Si (C 1 -C 8 alkyl) r (phenyl) 3-r ; Or < Lt; / RTI >
    n is from 1 to 20,
    r is 1, 2 or 3,
    R 9 is hydrogen, C 1 -C 12 alkyl, C 2 -C 12 alkenyl, cyclohexyl, or -OH, -SH, -CN, C 1 -C 4 alkoxy, C 3 -C 6 alkenoxy, OCH 2 CH 2 CN, -OCH 2 CH 2 COO (C 1 -C 4 alkyl), -OCO-C 1 -C 4 alkyl, -OCO-phenyl, COOH or COO (C 1 -C 4 alkyl) C 2 -C 6 alkyl; C 2 -C 12 alkyl substituted with one or more -O- or -S-; Phenyl unsubstituted or substituted with halogen, C 1 -C 12 alkyl or C 1 -C 4 alkoxy; Phenyl-C 1 -C 3 alkyl, Lt; / RTI >
    R 10 and R 11 are each independently selected from the group consisting of hydrogen, C 1 -C 12 alkyl, C 2 -C 4 hydroxyalkyl, C 2 -C 10 alkoxyalkyl, C 2 -C 5 alkenyl, C 5 -C 12 cycloalkyl Phenyl, phenyl-C 1 -C 3 alkyl, C 1 -C 12 alkyl, or phenyl unsubstituted or substituted with C 1 -C 4 alkoxy; Or C 2 -C 3 alkanoyl, C 3 -C 6 alkenoyl or benzoyl,
    R 10 and R 11 form together C 2 -C 6 alkylene optionally interrupted by -O- or -NR 8 -, or by hydroxyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoyloxy or benzoyl form a C 2 -C 6 alkylene which may be substituted with oxy or
    When R 10 is a hydrogen, R 11 is formula Lt; / RTI >
    R 12, R 13, R 14 , R 15, R 16, R 17, R 18 and R 19 each independently represent or more hydrogen, halogen, C 1 -C 12 alkyl, cyclopentyl, cyclohexyl, or one or OR 8, SR 9 or NR 10 R 11 ; Benzyl, benzoyl, C 2 -C 12 alkanoyl, C 2 -C 12 alkoxycarbonyl, optionally substituted with one or more -O-, and / or optionally substituted with one or more hydroxyl groups; Phenoxy carbonyl group or OR 8, SR 9, SOR 9 , SO 2 R 9, NO 2, CN, CONR 10 R 11 or NR 10 R 11 group (wherein the substituents OR 8, SR 9 and NR 10 R 11 is phenyl or the radicals R 8, R 9, with the R 10 and / or R 11 may form a 5- or 6-membered ring) together with one of the with the additional substituents present in the ring or a phenyl ring carbon atom,
    R 15 and R 16 together form ethylene or ethynylene,
    t is 0 or 1,
    M is C 1 -C 12 alkylene, cyclohexylene, phenylene, -COO- (C 2 -C 12 alkylene) -OOC-, -COO- (CH 2 CH 2 O) n -OC- or -CO - (C 2 -C 12 -alkylene) -CO-,
    M 1 is a direct bond or C 1 -C 12 alkyleneoxy optionally interrupted by 1 to 5 -O-, -S- and / or -NR 10 -
    M 2 is a direct bond or C 1 -C 12 alkylene-S- in which 1 to 5 -O-, -S- and / or -NR 10 - are optionally incorporated,
    M 3 is a direct bond or a piperazino group or C 1 -C 12 alkylene-NR 10 - optionally interrupted by 1 to 5 -O-, -S- and / or -NR 10 -
    M 4 is a direct bond or a group represented by -O-, -S-, -SO-, -SO 2 -, -CO-, -CH 2 -, -NR 10 - Lt; / RTI >
    Ar is a 5 or 6 membered aromatic heterocycle optionally substituted with one or more C 1 -C 6 alkyl, phenyl, halogen, OR 8 , SR 9 , NR 10 R 11 , CN, C 2 -C 6 alkanoyl or benzoyl Click ring,
    Except that 1-phenyl-1,2-propanedione-2-o-benzoyloxime and 1-phenyl-1,2-propanedione-2-o-ethoxycarbonyloxime are excluded.
    [2" claim-type="Currently amended] The method of claim 1, wherein in compounds of formula I and formula III, R 1 is one or more C 1 -C 6 alkyl, phenyl, halogen, OR 8, SR 9 or optionally substituted phenyl as NR 10 R 11, C 6 -C 20 alkyl or C 2 -C 20 alkyl optionally substituted with one or more -O- and / or optionally substituted with one or more hydroxyl groups.
    [3" claim-type="Currently amended] The composition of claim 1, wherein the oligomer or polymer (A) contains two or more polymerizable ethylenically unsaturated groups.
    [4" claim-type="Currently amended] The resin composition according to claim 1, wherein the oligomer or polymer (A) is a resin obtained by reacting a saturated or unsaturated polyfunctional acid anhydride with a reaction product of an epoxy compound and an unsaturated monocarboxylic acid, or a resin obtained by reacting a carboxyl group- And an unsaturated compound having an epoxy group.
    [5" claim-type="Currently amended] The composition of claim 1 comprising at least one photosensitizer compound (E) in addition to component (A), component (B), component (C) and component (D).
    [6" claim-type="Currently amended] The composition according to claim 3, which comprises 100 parts by weight of the component (A), 0.015 to 60 parts by weight of the component (B), 5 to 300 parts by weight of the component (C), 10 to 150 parts by weight of the component (D) 60 parts by weight.
    [7" claim-type="Currently amended] The composition according to claim 1, further comprising an additive (F) selected from the group consisting of an inorganic filler, a colorant, an epoxy curing agent, a thermal polymerization inhibitor, a thickener, an antifoaming agent and an antistatic agent, especially an inorganic filler.
    [8" claim-type="Currently amended] A solder resist comprising the composition according to claim 1.
    [9" claim-type="Currently amended] A method of photopolymerizing a compound having an ethylenically unsaturated double bond, comprising irradiating the composition according to claim 1 with a light beam in a range of 200 to 600 nm.
    [10" claim-type="Currently amended] Wherein at least one surface is coated with the composition according to claim 1.
    [11" claim-type="Currently amended] 11. A method of photographically manufacturing a relief image by image-exposing a coated substrate according to claim 10 and removing the unexposed part with a solvent.
    [12" claim-type="Currently amended] (1) mixing the components of the composition according to claim 1, (2) applying the resulting composition to a substrate, (3) evaporating the solvent present, and (4) (5) washing the irradiated sample with an alkaline aqueous solution to develop, and (6) thermally curing the sample to produce a solder mask.
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    同族专利:
    公开号 | 公开日
    CN1307693A|2001-08-08|
    BR9911572A|2001-03-20|
    WO2000000869A1|2000-01-06|
    DE69938305D1|2008-04-17|
    AU4773999A|2000-01-17|
    JP2002519732A|2002-07-02|
    US6485885B1|2002-11-26|
    TW484034B|2002-04-21|
    MY121423A|2006-01-28|
    DE69938305T2|2009-03-19|
    KR100563019B1|2006-03-22|
    AT388426T|2008-03-15|
    EP1095313B1|2008-03-05|
    CA2333365A1|2000-01-06|
    AU751966B2|2002-09-05|
    CN1203374C|2005-05-25|
    EP1095313A1|2001-05-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-06-26|Priority to EP98810596.1
    1998-06-26|Priority to EP98810596
    1999-06-18|Application filed by 에프. 아. 프라저, 에른스트 알테르 (에. 알테르), 한스 페터 비틀린 (하. 페. 비틀린), 피. 랍 보프, 브이. 스펜글러, 페. 아에글러, 시바 스페셜티 케미칼스 홀딩 인크.
    2001-06-25|Publication of KR20010053101A
    2006-03-22|Application granted
    2006-03-22|Publication of KR100563019B1
    优先权:
    申请号 | 申请日 | 专利标题
    EP98810596.1|1998-06-26|
    EP98810596|1998-06-26|
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