JPH04204438A - High molecular photosensitizer - Google Patents

Abstract

PURPOSE:To ensure high sensitivity to a light source having a strong emission spectrum at long wavelength side and to increase sensitivity even when a pigment is added by incorporating a specified structure into the side chain of a high molecular compd. CONSTITUTION:A structure represented by formula I is incorporated into the side chain of a high molecular compd. In formula I, R1 is 1-10C divalent hydrocarbon which may contain at least one among ester, ether and urethane bond in the chain and each of X and Y is at least one among H, halogen, 1-10C alkyl, alkenyl, 6-10C aryl, aralkyl, alkoxy, alkoxycarbonyl and cyano. A high molecular photosensitizer ensuring high sensitivity to light having long wavelength and nearly independent of light absorption by a pigment such as titanium oxide is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a photosensitizer for photosensitive resin compositions used in paints, printing inks, printing materials such as letterpress plates and planographic plates.

[Conventional technology] Conventionally, radicals are generated by irradiation with ultraviolet rays,
There are many known photosensitizers that can act as polymerization initiators for monomers having radically polymerizable ethylenically unsaturated bonds, among which hensifhenone, Michler's ketone, fluorenone, xanthone, and thioxanthone are well known. It is being However, when these compounds are used as photosensitizers in photosensitive resin compositions, due to the structure of these compounds, they are not sufficiently sensitive to light sources with a strong emission spectrum on the long wavelength side, such as metal halide lamps. Moreover, in systems containing pigments such as titanium oxide, the absorption spectrum of the pigment and the absorption spectrum of the photosensitizer overlap, so it is difficult to determine the amount of light at the wavelength necessary for the photosensitizer. There is a problem that the sensitivity decreases and the sensitivity does not increase.

In addition, JP-A-61-145203 discloses a halogen-substituted acridone photosensitizer that has high sensitivity to long wavelength light, is less affected by light absorption by pigments such as titanium oxide, and has excellent storage stability. agent is indicated. However, these photosensitizers have low molecular weights, and some of them volatilize when the photosensitive composition is applied at high temperatures, or some of them migrate to the primer layer when a primer layer is provided. Therefore, there is a problem in that in order to bring out its effects, it must be added in an amount greater than the required amount.

“Problems to be Solved by the Invention” The present invention solves the problems that the sensitivity to light sources having a strong emission spectrum on the long wavelength side is low, and the sensitivity does not increase when pigments are added, When applying the photosensitive composition at high temperatures, some of it may evaporate,
This is an attempt to solve the problem of having to add more than the necessary amount to bring out the effect because some of it migrates to the primer layer.

[Means for Solving the Problems 1] As a result of studies to solve these problems, the present inventors found that a polymer having an acridone group with a specific structure in its side chain,
It has high sensitivity to long wavelength light, is less affected by light absorption by pigments such as titanium oxide, and has excellent storage stability.
When applying the photosensitive composition at high temperatures, part of it does not volatilize, and if a primer layer is provided, part of it does not migrate to the primer layer, so it is added only in the amount necessary to bring out the effect. The present invention was achieved by discovering that scales can be used as photosensitizers that only need to be treated.

That is, the present invention relates to a polymer photosensitizer containing a structure represented by the following general formula (D) in its side chain.

(However, R1 is a divalent hydrocarbon group having 1 to 10 carbon atoms and may contain at least one selected from ester, ether, and urethane bonds in the chain. X and Y are each hydrogen It represents at least one selected from atoms, halogen, alkyl groups having 1 to 10 carbon atoms, alkenyl groups, aryl groups having 6 to 10 carbon atoms, aralkyl groups, alkoxy groups, alkoxycarbonyl groups, and cyano groups. ) The polymer photosensitizer used in the present invention (7) has the general formula (
Any polymer compound containing the structure represented by I) may be used.

For example, those having a structure as shown in formula (II) can be mentioned.

-R2-R3- R2 and R3 are main chain structures, and R2 is R4R6R
6R6 II l 1 -C-, -N-C-, -N-, -C-N-.

l II R500 -C--C-O- Nato is mentioned.

As R3, R7R7R7 And so on.

(Here, R4, R5, R7 are a hydrogen atom, a halogen, a hydroxyl group, an amino group, a cyan group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkoxy group, an aminoalkyl group,
Mercaptoalkyl group 1, haloalkyl group, hydroxyalkyl group, carboxyalkyl group having 2 to 10 carbon atoms,
A cyanoalkyl group, an optionally substituted aryl group having 6 to 10 carbon atoms, or an aralkyl group, each of which may be the same or different. R6 is a hydrogen atom or an alkyl group having 1 to 1 o carbon atoms. ) Specific examples of the structure of the main chain include polyester, polyether, polyurethane, polyamide, polystyrene, polycarbonate, polyacrylate, and polymethacrylate, with polystyrene, polyacrylate, and polymethacrylate being particularly preferred.

Specific examples include the following (1) to (2).

A polymer of the compound represented by H2 or a copolymer with other styrenic monomers or (meth)acrylic acid esters.

A ring-opening polymer of the compound represented by or a co-ring-opening polymer with another epoxy compound.

■ CH2CH20CC= CI 2(R8
is a hydrogen atom or a methyl group. ) or a copolymer with other (meth)acrylic acid esters or styrenic monomers.

(2) Polymers of compounds represented by OH CH2CHCH20CC=CH2 (R8 is the same as above) or copolymers with other styrenic monomers or (meth)acrylic acid esters.

■■ (R8 is the same as above.) A polymer of the compound represented by (R8 is the same as above) or a copolymer with other (meth)acrylic acid ester or styrene monomer.

■ A polyurethane made of a polyester made of a compound represented by HOCH2CHOH H2 and a dicarboxylic acid, or a diisocyanate compound.

The polymer photosensitizer containing the structure represented by the general formula (I) of the present invention in its side chain can also be used in combination with known photosensitizers and photosensitizers.

Such photosensitizers include hensifhenone, fluorenone, xanthone, thioxanthone, 2-chlorothioxanthone, 4,4-bis(dimethylamino)hensiphenone, 4,4-bis(diethylamino)benzophenone, and the like. , 4,4-monohis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)hensiphenones, and other his(dialkylamino)hensiphenones are effective. As a photosensitizer, N,N--ethyl dimethylaminobenzoate, N,N--methyl dimethylaminobenzoate, N,N
---Amines such as 2-ethylhexyl dimethylaminobenzoate, triethanolamine, and N-methyljetanolamine may be mentioned.

The photosensitizer of the present invention is a photosensitizer component of a thin-film photosensitive coating composition containing one or more of monomers, prepolymers, and polymers having radically polymerizable ethylenically unsaturated bonds. Particularly excellent effects are shown when

The thin film property here refers to the film thickness of the photosensitive coating, which is 011μ~
It means 100μ.

The monomer, prepolymer, or polymer having a radically polymerizable ethylenically unsaturated bond, which is an essential component of the thin-film photosensitive coating composition, may be any known compound having an acroyl group or a methacryloyl group with a boiling point of 100°C or higher. Here are some good and typical examples:

(I) Acrylic acid or methacrylic acid ester of the following alcohols.

Methanol, ethanol, propatool, hexanol, octatool, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol,
triethylene glycol, tetraethylene glycol,
Polyethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.

(2) A reaction product of the following amines or carboxylic acids with glycidyl acrylate or lycidyl methacrylate.

Methylamine, ethylamine, butylamine, benzylamine, ethylenediamine, diethylenetriamine, hexamethylenediamine, p-xylylenediamine, m-
Xylylene diamine, ethanolamine, dimethylamine, aniline, etc.

Acetic acid, propionic acid, benzoic acid, acrylic acid, methacrylic acid, succinic acid, maleic acid, phthalic acid, tartaric acid, citric acid, etc.

(3) Amide derivatives as shown below.

Acrylamide, methacrylamide, N-methylolacrylamide, methylenebisacrylamide, diacetone acrylamide, etc.

(4) A reaction product of a poxy compound and acrylic acid or methacrylic acid.

(5) A reaction product of an isocyanate-containing compound and β-hydroxyethyl acrylate or β-hydroxyethyl methacrylate.

One or more of these compounds are used as a constituent component,
Furthermore, if necessary, it is also possible to add an organic polymer compound that can be mixed with these compounds.

Examples of such organic polymer compounds include the following polymers and copolymers.

(I) Polymers of acrylic esters, methacrylic esters, acrylonitrile, such as polyethyl acrylate, polybutyl acrylate, polymethyl methacrylate, etc., and copolymers thereof.

(2) Unvulcanized rubber, such as polybutadiene, polyisobutylene, polychloroprene, styrene-butadiene rubber, etc.

(3) Vinyl polymers, such as polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, etc., and copolymers thereof.

(4) Polyethers, such as polyethylene oxide.

(5) Polyesters, such as phthalic acid, isophthalic acid,
Maleic acid, adipic acid, etc. and ethylene glycol, 1
, 4-butanediol, 1,6-hexanediol, neopentyl glycol, and other reaction products.

(6) polyurethane, such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, etc. and 1,4-butanediol, 1,6-hexanediol,
A reaction product with the polyether polyol of (4), the polyester polyol obtained in (5), etc.

(7) Epoxy resin (8) Polyamide thin film photosensitive coating composition preferably contains 100 parts by weight of one or more of the radically polymerizable ethylenically unsaturated bond-containing monomer, prepolymer, and polymer. Adds 1 to 5'00 parts by weight of an organic polymer compound,
Obtained by adding 0.5 to 50 parts by weight of a polymer photosensitizer containing the structure represented by the general formula (I) in its side chain, and 1 to 50 parts by weight of other photosensitizers if necessary. It will be done.

In addition to the above-mentioned components, additives such as dyes, pigments, and polymerization inhibitors can be added as necessary.

As a preferable application example in which the polymer containing the structure represented by the general formula (I) in the side chain of the present invention is used as a photosensitizer, an upper layer or a lower layer of the thin photosensitive coating obtained as described above is used. Add a silicone rubber layer to 0. 5~50μ
A waterless lithographic printing plate material obtained by forming a film with a film thickness of .

The silicone rubber used here has the following general formula (II
A typical example is one obtained by crosslinking the linear organopolysiloxane shown in I).

Sound-(-3iO@□□・・・・・・・・・・□T(III)R
IO (wherein R9 and RIO are substituted or unsubstituted alkyl groups or alkenyl groups having 1 to 10 carbon atoms, substituted or unsubstituted aryl groups having 6 to 10 carbon atoms, especially methyl groups or (N is an integer of 2 or more.) A general method for crosslinking linear organopolysiloxanes is to crosslink linear organopolysiloxanes by using a silicon compound containing a hydrolyzable functional group directly bonded to a silicon atom. Examples include methods of cross-linking, especially those with molecular weight ioo having a silanol structure at the end.

A silicon compound having ~1 million organopolysiloxanes and two or more functional groups such as alkoxy groups, acyloxy groups, ketoximate groups, amide groups, aminooxy groups, amino groups, alkenyloxy groups, and hydrogen groups directly bonded to silicon atoms. A commonly used method is to cure the rubber by reacting with the rubber. In addition, with radical initiators,
It is also possible to cure organopolysiloxanes to form rubber. In these curing processes, addition of known catalysts is optional.

[Example] The present invention will be explained in detail below with reference to Examples.

Synthesis Example 1 0 CH2Cl 10 g of acridone and 2 g of NaH were reacted in 100 g of dimethylformamide (hereinafter abbreviated as DMF) at o 0C for 2 hours. Then add 11.4-chloromethylstyrene into this solution at 0°C. ．． 5 g was added dropwise little by little, and after the dropwise addition was completed, the reaction was carried out at 0° C. for 2 hours.

To 5 g of the styrene derivative monomer synthesized in this way, 0.05 g of 2.2'-azohis(isobutyronitrile) (hereinafter abbreviated as AIBN) was added, and radical polymerization was carried out in methyl isobutyl ketone (hereinafter abbreviated as MTBK) to obtain an average molecular weight of 5
0000 polymer photosensitizer (I) was obtained.

Synthesis Example 2 I 10 g of 2-bromoacridone and 81 g of N'a were added to DMFL
The reaction was carried out for 2 hours at 0° C. in OOg. Next, add 0 to this solution.
5.7 g of shrimp bromohydrin was added dropwise little by little at 0.degree. C., and after the addition was completed, the mixture was reacted at 0.degree. C. for 2 hours.

5 g of the epoxy monomer thus synthesized was subjected to ring-opening polymerization using 0.05 g of diethylzinc catalyst to obtain a polymer photosensitizer (II) having an average molecular weight of 20,000.

Synthesis Example 3 CH2CH20H CH2CH20H CH2CH20CCH= CH2 2-Rioroacrytone Log and Na H2g in DMF
The reaction was carried out in 100 g at 0° C. for 2 hours. Next, 1 g of bromoethanol was added dropwise little by little into this solvent at 0°C, and after the dropwise addition was completed, the reaction was carried out at 0°C for 2 hours. The obtained N-(
2-hydroxyethyl)-2-chloroacridone 5g, acrylic acid chloride 2.5g, triethylamine 5g
g and tetrahydrofuran (hereinafter abbreviated as THF) 10
The reaction was carried out in 0 g at room temperature for 5 hours.

5gJ of the acrylic monomer synthesized in this way, :AIBN
0.05 g was added and radical polymerized in M1BK to obtain a polymer photosensitizer (III) with an average molecular weight of 60,000.

Synthesis Example 4 I OCI CH20H H2 10g of 2-cyanoacridone and 2g of NaH in DMF
The reaction was carried out in 100 g at 0° C. for 2 hours. Next, 6 g of 3-chloro-1,2-propanediol was added dropwise little by little into this solution at OoC, and after the completion of the dropwise addition, the reaction was carried out at 0° C. for 2 hours.

The diol thus obtained was copolymerized with adipic acid to obtain a polymer photosensitizer (IV) with an average molecular weight of 20,000.

Example 1 A photosensitive coating composition having the following composition was applied onto a tin plate using an applicator and heat treated at 150°C for 5 minutes to form a 20μ thick film.

(a) N, N, N-, N--tetrakis-2-hydroxy-3-methacroyloxypropylethylenediamine (4.
1 molar ratio reactant) 100 parts by weight (b) 150 parts by weight of "Vandex" T-5201 (polyurethane resin manufactured by Dainippon Ink & Chemicals Co., Ltd.) (C) Polymer photosensitizer (I) 10 parts by weight (
d) DMF 800 parts by weight When this film was irradiated with light from a 2 kW metal halide lamp from a distance of 50 cm in air, the film lost its stickiness in 50 seconds and curing was completed.

Comparative Example 1 Films were created by changing the polymer photosensitizer (I) in Example 1 to benzophenone and xanthone, respectively, and irradiated with light from a distance of 50 cm using a 2 kW metal/1 light lamp in the same manner as in Example 1. However, when the number of seconds until the film lost its tackiness was measured, it was 450 seconds in the case of benzophenone and 150 seconds in the case of xanthone.

This table shows that the sensitivity to the metal halide lamp is higher (the time required until the tackiness disappears is shorter) when the polymer photosensitizer (I) is used.

Comparative Example 2 When a film was prepared by changing the polymer photosensitizer (I) in Example 1 to N-methylacridone and exposed in the same manner as in Example 1, the film lost its tackiness, but It took 65 seconds. When the amount of N-methylacridone in the coating film was analyzed, it was found that the amount of N-methylacridone was reduced by 5% from the amount initially added, indicating that some of it evaporated during coating.

It can be seen that higher sensitivity can be obtained when using the polymer photosensitizer (I).

Example 2 The polymer photosensitizer (I) of Example 1 was replaced with the polymer photosensitizer (n
), and when exposed in the same manner as in Example 1, the tackiness of the film disappeared in 50 seconds.

Example 3 The polymer photosensitizer (I) of Example 1 was replaced with the polymer photosensitizer (m
) was prepared and exposed in the same manner as in Example 1, and the film became sticky in 45 seconds.

Example 4 A 6μ thick photosensitive film having the following composition was formed on an aluminum plate.

Apply on raw board using applicator and apply 150(a)
N, N, N-, N-tetrakis-2-hydroxy-3
-Methacroyloxypropyl-m-xylylenediamine (4:1 molar ratio reaction product of chrysinyl methacrylate and m-xylylenecyamine)
ioo parts by weight (b) “Vandex” T-52
01 (polyurethane resin manufactured by Dainippon Ink and Chemicals Co., Ltd.) 160 parts by weight (C) Polymer photosensitizer (III) 15 parts by weight (d) 4.4'-bis(diethylamino)benzophenone 10 parts by weight A silicone gum solution having the following composition was applied onto the rubber coating and dried to form a silicone rubber layer with a thickness of 3 μm.

(a) Polydimethylsiloxane with silanol groups at both ends (
Average molecular weight: 35,000) 100 parts by weight (b) 12 parts by weight of ethyltriacetoxysilane (C) Dibutyltin diacetate 0. 2 parts by weight (d
) n-Hebutane 1200 parts by weight A 12 μm thick polyethylene terephthalate film “Lumirror” (manufactured by Toshi) was laminated on the surface of the silicone rubber layer thus obtained using a calendar roller to obtain a waterless planographic plate material. 1 to 1 on this plate material using a vacuum printing frame.
A sensitivity management film "Fuji PS Step Guide" (manufactured by Fuji Photo Film ■), which has a density difference of 0.15 or 1 step in 5 steps, is closely attached, and the light from a 2 kW metal/1 light lamp is transmitted over a distance of 1 m. Irradiated for 60 seconds from a distance.

Peel off the protective film “Lumirror” and remove the exposed plate.
- When rubbed lightly with a pad soaked in hebutane, the parts of the photosensitive film where a photoreaction has occurred are strongly adhered to the silicone rubber layer (photoadhesion), whereas the parts of the photosensitive film where no photoreaction has occurred The adhesion to the silicone rubber layer is weak in this area, and the silicone rubber layer is peeled off, exposing the photosensitive coating. When I read the highest value of StepKite on the part where this silicone rubber layer is optically bonded, it was 8. This value will be referred to as sensitivity hereinafter, and the higher the value, the higher the sensitivity.

Comparative Example 3 The polymer photosensitizer (II[) of Example 4 was changed to 4,4″-bis(diethylamino)benzophenone, and 4.4′
- A waterless lithographic printing plate material containing only bis(diethylamino)benzophenone as a photosensitizer was prepared in the same manner as in Example 4. When exposed and developed in the same manner as in Examples, the sensitivity was 2.

Example 5 The polymer photosensitizer (n) of Example 4 was replaced with the polymer photosensitizer (I
A waterless lithographic printing plate material was prepared in the same manner as in Example 4 except for V). When exposed and developed in the same manner as in Example 4, the sensitivity was 9.

[Effects of the Invention] Since the present invention is constructed as described above, the sensitivity to long wavelength light is high, the influence of light absorption by pigments such as titanium oxide is small, the storage stability is excellent, and the photosensitive composition can be used at high temperatures. Polymer light does not partially volatilize when applied, and does not migrate to the primer layer if a primer layer is provided, so you only need to add the necessary amount to bring out the effect. A sensitizer can be obtained.

Claims (1)

[Scope of Claims] 1. A polymer sensitizer characterized by containing a structure represented by the following general formula (I) in its side chain. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R1 is a divalent hydrocarbon group having 1 to 10 carbon atoms and may contain at least one selected from ester, ether, and urethane bonds in the chain. .X and Y are each at least one selected from a hydrogen atom, a halogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an aryl group having 6 to 10 carbon atoms, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, and a cyano group. )