JPS59202458A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To increase the curability of a photosensitive composition contg. a compound having an ethylenic unsatd. bond as a photopolymerizable component in the presence of oxygen by adding a thiophosphate compound to the composition. CONSTITUTION:This photosensitive composition contains a radical polymerizable ethylenic unsatd. compound and 0.01-20wt% thiophosphate compound represented by the general formula. In the formula, each of R1, R2 and R3 is 1-20C alkyl, aryl or aralkyl, it may have halogen, 1-20C alkoxy, a alkoxycarbonyl, acyloxy, alkanoyl, cyano, hydroxyl or amino as a substituent, X is 0 or -CR4R5-, each of R4 and R5 is H, 1-20C alkyl, aryl or aralkyl, each of m and n is 0, 1, 2 or 3, p is 0, 1 or 2, and m+n+p=3.

Description

[Detailed Description of the Invention] Technical Field The present invention relates to a photosensitive composition containing a compound having a radically polymerizable ethylenically unsaturated bond as a photopolymerizable component, and is particularly used in the fields of printing plates and the like. be.

<Prior art> Photosensitive compositions containing radically polymerizable ethylenically unsaturated bonds as a photopolymerizable component are widely used in printing plates (letterpress or lithography), paints, inks, photoresists, etc. Since polymerization of radically polymerizable compounds having ethylenically unsaturated bonds is inhibited by oxygen, there is a problem in that curing properties are poor in the presence of oxygen.

In order to improve this point, improvements have been made to compounds with radically polymerizable ethylenically unsaturated bonds, and it has been proposed to introduce amino groups, urethane groups, etc. into the molecule. 41 708, 49-1 38
70 is not enough.

<Object of the Invention> As a result of intensive studies to improve the curability in the presence of oxygen, the present inventors have developed a photosensitive material using a compound having a 9-radically polymerizable ethylenically unsaturated bond as a photopolymerization component. By containing a thiophosphite compound in a chemical composition, the thiophosphite compound rapidly reacts with oxygen when activated by light and consumes oxygen in the system, resulting in radically polymerizable ethylene. Polymerization of compounds having sexually unsaturated bonds is no longer inhibited. That is, the inventors have discovered the fact that the curability of the composition in the presence of oxygen is significantly enhanced, and have thus arrived at the present invention.

<Configuration of the Invention> The configuration of the present invention includes a radically polymerizable ethylenically unsaturated compound and a thiophosphite compound represented by the following general formula.
It is a photosensitive composition characterized by containing 1 to 20% by weight.

(R,, R,, R, is a C6 to C3 alkyl group, aryl group, aralkyl group, and these have substituents and halogen, 01 to C20 alkoxy group, alkoxycarbonyl group, acyloxy group, alkanoyl group, It may have a cyano group, a hydroxyl group, or an amine group. ,
n is an integer of 0 to 3, p is an integer of O to 2, m+n+
p=3)0 Compounds having one or more radical or ethylenically unsaturated bonds in the molecule that can be used in the present invention include the following.

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

Methanol, ethanol, propatool, hexanol, octatool, cyclohexanol.

Ethylene glycol, tetraethylene glycol.

Polyethylene glycol, propylene glycol.

Dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, bisphenol A with ethylene oxide, etc.

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

Methylamine, ethylamine, butylamine.

Benzylamine, ethylenediamine, diethylenetriamine, hexamethylenediamine, p-xylylenediamine, m-xylylenediamine, ethanolamine, dimethylamine, diethylamine.

jetanolamine, aniline, etc.

Acetic acid, propionic acid, benzoic acid, acrylic acid.

Methacrylic acid, succinic acid, maleic acid, phthalic acid.

such as tartaric acid.

(3) Amide derivatives as shown below.

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

(4) A reaction product of an epoxy compound and acrylic acid or methacrylic acid.

(5) A reaction product between an inocyanate-containing compound and a hydroxyl group-containing acrylic ester or methacrylic ester.

(6) Ammonium salt or metal salt of acrylic acid or methacrylic acid.

In the present invention, a compound having one or more radical ethylenically unsaturated bonds in the molecule as described above is used, but in addition to this, the following polymers soluble in water or ordinary organic solvents may also be used. can be done. Polymers soluble in water or ordinary organic solvents include the following.

(1) Polymers of acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylonitrile, and copolymers thereof. For example, polyethyl acrylate, polymethyl methacrylate.

Butyl polyacrylate.

(2) Unvulcanized rubber. For example, polybutadiene, polyisobutylene and styrene-butadiene rubber.

(3) Polyvinyl alcohol derivative. For example, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, partially saponified polyvinyl acetate, etc.

(4) Polyether. For example, polyethylene oxide, polypropylene oxide, etc.

(5) Polyester. For example, reaction products of phthalic acid, isophthalic acid, maleic acid, adipic acid, etc. with ethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.

(6) Polyurethane. For example, toluene diisocyanate, hexamethylene diisocyanate, toinphorone diisocyanate, diphenylmethane diisocyanate,
A reaction product of 1,4-butanediol, 1°6-hexanediol, the polyether polyol of (4), the polyester polyol obtained in (5), etc.

(7) Epoxy resin.

(8) Polyamide. For example adipic acid, sepatic acid, azelaic acid and hexamethylene diamine.

Reaction products with l.dimethylhexamethylene diamine, 4,4/-diaminocyclohexylmethane, etc.

Polymers such as ε-caprolactam and ω-aminoundecanoic acid.

(9) Cell o-sm conductor. fc toe itf,
Cellulose acetate, cellulose acetate butyrate, etc.

Furthermore, in the present invention, a compound in which a radically polymerizable ethylenically unsaturated bond is introduced into the above-mentioned soluble polymer by a known method is a compound having "one or more" two radically polymerizable ethylenically unsaturated bonds in the molecule. It can also be used as Examples of such compounds include the following.

(1) A reaction product of a polymer of (meth)acrylic acid glycidyl ester or a copolymer with another (meth)acrylic acid ester and (meth)acrylic acid.

+21 A reaction product of a polymer of a (meth)acrylic ester containing a hydroxyl group or a copolymer with another (meth)acrylic ester and a (meth)acrylic ester containing an isocyanate group.

(3) A reaction product between epoxidized polybutadiene and (meth)acrylic acid.

(4) A reaction product of a polyurethane having an isocyanate group in its molecule and a hydroxyl group-containing (meth)acrylic ester.

(5) A reaction product of a polyurethane having a hydroxyl group in its molecule and a (meth)acrylic acid ester having an isocyanate group.

(G) A reaction product between an epoxy resin and (meth)acrylic acid.

(7) Reaction product of N-oxy or N-alkoxy polyamide and (meth)acrylic acid.

(8) A reaction product of polyamide and (meth)acrylic acid glycidyl ester.

These polymers preferably contain two or more radically polymerizable ethylenically unsaturated bonds in one molecule.

In addition to the above-mentioned essential components, the photosensitive resin composition of the present invention contains stabilizers such as photopolymerization initiators, photosensitizers, and thermal polymerization inhibitors, compatibility improvers, dyes, pigments, fillers, etc. You can leave it there. By adding a photopolymerization initiator and a photosensitizer, a highly sensitive photosensitive resin composition can be obtained. As such photopolymerization initiators and photosensitizers, the following can be used.

Benzoin methyl ether, penzoin isof.

Lobil ether, benzoin derivatives such as α,a-dimethoxy-α-phenylacetophenone, benzophenone, 2,4-dichlorobenzophenone.

Benzophenone derivatives such as methyl O-benzoylbenzoate, 4,4/-bis(dimethylamino)benzophenone, 4.4/-bis(diethylamine)benzophenone, thioxanthone derivatives such as 2-chlorothioxanthone, 2-inpropylthioxanthone, 2 - Anthraquinone derivatives such as chloranthraquinone and 2-methylanthraquinone, acridone derivatives such as N-methylacridone and N-butylacridone, a,α-jethoxyacetophenone, benzyl, fluorenone, and xanthone.

Uranyl compounds, norogen compounds, etc.

In the present invention, the thiophosphite compound added for the purpose of improving curability in the presence of oxygen has the structure of the first-order general formula (I).

(R,, R,, R, is a C1-C20 alkyl group, aryl group, aralkyl group, and substituents for these include halogen, C3-C2° alkoxy group, alkoxycarbonyl group, acyloxy group, alkanoyl group, May have a cyano group, hydroxyl group, or amino group. -X- is -0
-, -CR,R,-, 'R, + Rs is hydrogen,
The alkyl group, aryl group, and aralkyl group of 01 to Cto are shown. H, n is an integer of 0 to 3, pr.

2, where m+n+p=3).

Examples of these compounds include the following: Tributyltrithiophosphite.

Trioctyl trithiophosphite, trilauryl trithiophosphite, tributyl trithiophosphite,
Tri(o-1lyl)trithiophosphite, tribenzyltrithiophosphite.

Tri(2-methoxyethyl)trithiophosphite, tri(ethoxycarbonylmethyl)trithiophosphite, tri(butoxycarbonylmethyl)trithiophosphite, tri(octyloxycarbonylmethyl)trithiophosphite, tri(ro-methoxybutyloxycarbonyl) methyl)trithiophosphite, tri(β-ethoxycarbonylenyl)trithiophosphite, tri(
β-butoxycarbonylethyl)trithiophosphite, tri(β-octyloxycarbonylethyl)trithiophosphite, tri(β-6-medoxybutyloxycarbonylethyl)trithiophosphite, tri(β-
acetoxyethyl)trithiophosphite, tri(β-
cyanethyl) trithiophosphite, dilauryl dithiobutyl phosphite, dibutyl ethyl thiophosphonite, lauryl diptyl thiophosphinate, etc.

What is the amount of these thiophosphite compounds added?

The amount is 0.001 to 20% by weight, preferably 0.05 to 10% by weight, based on the photosensitive composition. If the weight ratio is less than 0.01, the effect of improving curability in the presence of oxygen is small.

Moreover, if the weight exceeds 20, it becomes difficult to maintain the shape.

The photosensitive composition that is the subject of improvement in the present invention.

It is used as a material for printing plates (letterpress or lithography), paints, inks, photoresists, etc., and is particularly preferably used for thin films. Furthermore, a silicone rubber layer of 0.5 to 50 μm is applied as an upper or lower layer of the film of this photosensitive composition.
A photosensitive plate material for lithographic printing that does not require dampening water can be obtained by providing the film with a film thickness of It is obtained by sparsely crosslinking a polysiloxane (preferably dimethylpolysiloxane). A typical silicone rubber has nine repeating units.

Here, n is an integer of 2 or more.

R and R' are hydrogen and an alkyl group having 1 to 10 carbon atoms.

They are an aryl group and a vinyl group. Such silicone rubbers can be sparsely crosslinked by adding organic peroxides, but silicone rubbers that undergo net crosslinking (
A more preferable silicone rubber film can be obtained by using a silicone rubber (RTV, LTV type silicone rubber). Such mesh type silicone rubber is usually crosslinked by the following condensation of end groups. In some cases, an excess of crosslinking agent may be present.

(R'2C=N-O+Si-〇-R is hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group,
It represents a vinyl group, and R/ is an alkyl group having 1 to 10 carbon atoms. AC represents an acetyl group.

The present invention will be described in detail below with reference to Examples.

Example 1. Comparative Example 1 A photosensitive resin composition containing a thiophosphite compound and a photosensitive resin composition not containing a thiophosphite compound having the following compositions were applied onto a tin plate using an applicator to a thickness of 10 microns. .

(a) 52 parts by weight of Pandex T-5201J (polyurethane resin manufactured by Dainippon Ink and Chemicals) (b) 45 parts by weight of trimethylolpropane triacrylate (c) 6 parts by weight of 2-chlorothioxanthone (
d) Thiophosphite compound 6 parts by weight This film was irradiated with light from a 3 kW high-pressure mercury lamp from a distance of 1 m in air, and the number of seconds until the film lost its tackiness was taken as a measure of curability.

The results are shown in Table 1.

Table 1 As is clear from Table 1, compositions 2 to 7 to which a thiophosphite compound was added were compared to composition 1 to which no thiophosphite compound was added.

Good curability under air.

Example 2. Comparative Example 2 A photosensitive resin composition having the following composition was laminated on a sheet la aluminum plate to a thickness of 0.5 mm to obtain a photosensitive resin plate.

(a) [Ultramid ICJ (BASF alcohol-soluble nylon 60 parts by weight) (b) N, N
, N',N'-tetrakis-2-hydroxy-6-methacroyloxypropyl-xylylenediamine (4/1 molar ratio reaction product of methacrylic acid glycidyl ester and m-xylylenediamine amine)
28 parts by weight (C) methacrylic acid-2-
Hydroxyethyl 10 parts by weight (d) Benzophenone 2 parts by weight (e)
) (2 parts by weight of octyloxycarbonylmethyltrithiophosphite) A 21-level gray scale manufactured by Stouffer was placed on this photosensitive resin plate.
Climb to 00w super high pressure mercury lamp.

Exposure was performed for 1 minute from a distance of 4'Ocm. Clean the unexposed areas by spraying this with methanol/triclene (80/20) for 2 minutes. When removed, the gray scale part was hardened to N119.

When a photosensitive resin plate containing no thiophosphite compound was prepared using a similar method, exposed to light, and washed, the polymerization was inhibited by the oxygen present in the system, and it was only cured up to N1111 on the gray scale. I hadn't.

Example 3, Comparative Example 6 A 6 micron thick photosensitive resin film having the following composition was formed on an aluminum plate.

(a) Copolymer of ethyl acrylate and methyl methacrylate (molar ratio 7:3, average molecular weight 50,000) 50 parts by weight (1)) N, N, N', N'-tetrakis-2
-Hydroxy-3-methacroyloxy-m-quinrylenediamine 60 parts by weight (c) Triethylene glycol dimethacrylate 14 parts by weight (a) 4,4'-bis(diethylamino)benzophenone 4 parts by weight (e)
2 parts by weight of fluorenone (f) 5 parts by weight of tri(β-octyloxycarbonylethyl)trithiophosphite
yg, -3085J (RTV Silicone Gum Dispersion manufactured by Toshiba Silicone ■) was diluted with n-hebutane and applied.

After drying, a silicone rubber i having a thickness of 25 microns was obtained. The silicone gum used in this example is a linear diorganopolysiloxane having an acetoxy group at the end.
Due to the action of moisture in the air.

Crosslinking occurs with the release of acetic acid, giving a rubbery coating. The surface of the silicone rubber layer thus obtained was laminated with a 12 micron thick polyethylene terephthalate film "Lumirror" (manufactured by Bunshishi ■) with a calendar roller to form a photosensitive plate material for lithography that does not require dampening water. did.

Using a vacuum printing frame, print 0 on this plate at 150 lines/inch.
A positive film having a dot area ratio of 5 to 995 was placed in close contact with the film, and irradiated with light from a 3 kW high-pressure mercury lamp for 60 seconds from a distance of Kl-1 m. The protective film "Lumirror" was peeled off, and the film was developed by immersing it in n-hebutane and rubbing it lightly with gauze. Only the part of the photosensitive coating where photopolymerization has occurred is strongly adhered to the silicone rubber layer (known as photoadhesion) and cannot be peeled off.

Only the silicone rubber layer other than this (the part where photoadhesion has not occurred) is peeled off, and the photosensitive coating is exposed. When evaluating the halftone + lS male of the developed version,
Halftone dots of 0.05 to 995% were visible.

Using a method similar to this, a photosensitive plate material for lithographic printing that does not contain a thiophosphite compound and does not require dampening water was prepared.

Exposure and development were performed. When the halftone dot reproduction 1'' of the developed plate was evaluated, it was found that 0.5 to 95% of the halftone dot 1 did not appear due to polymerization inhibition due to oxygen present in the system.

Claims (1)

[Scope of Claims] A photosensitive composition comprising a radically polymerizable ethylenically unsaturated compound and a thiophosphite compound represented by the following general formula in an amount of 0.01 to 20% by weight. (R1, R2, R are C,, -+C, .alkyl group, aralkyl group, and as substituents to these, halogen I Cl to C, .alkoxy group, alkoxycarbonyl group, acyloxy group, alkanoyl group, May have a cyan group, hydroxyl group, or amine group.X is 0 or 1C
R, R, -, and R4, R, are hydrogen. C1
~C,. Indicates an alkyl group, an aryl group, and an aralkyl group. m, n are integers from 0 to ro, p is an integer from 0 to 2,
m+n+p=3).