JPS6015428A - Photosensitive composition - Google Patents

Abstract

PURPOSE:A photosensitive composition of excellent photocurability which is not oxidized even after a long-period storage, comprising a polyene, a polythiol, and a specified thiophosphite compound. CONSTITUTION:0.01-2wt% thiophosphite compound of the formula (wherein R1-3 are each 1-20C alkyl, aryl, or aralkyl which may have substituents such as halogen, 1-20C alkoxy, alkoxycarbonyl, acyloxy and cyano groups, X is -O-, or -CR4R5-, R4 and R5 are each H, 1-20C alkyl, aryl, or aralkyl, m and n are each 0-3, p is 0-2, and m+n+p is 3) is added to a photopolymerizable composition comprising a polyene of a MW of 200-100,000 (e.g., trimethylolpropane triallyl ether), a polythiol [e.g., pentaerythritol tetrakis(beta-thiopropionate)] and, if required, a photopolymerization initiator, photosensitizer, filler, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a photosensitive composition containing a polyene compound or a polythiol compound as a photocurable component, and is particularly used in the fields of printing plates, paints, inks, etc.

[Prior art]

Photosensitive compositions containing a polyene-polythiol compound as a photocuring component are well known (for example, Japanese Patent Publication No. 46-29
525).

It is also known that addition of phosphine compounds to this system significantly improves photocurability.

(: Jouz-nal of Polymer 5ci
ence: PoymerLetterSEdit
ion 16. 75 (1978)) However, compositions with added bosphine compounds.

There is a problem in that the phosphine compound undergoes air oxidation during storage and loses its effectiveness.

[Purpose of the invention]

The present inventors have conducted intensive studies on a photocuring accelerator that improves the photocurability of polyene-polythiol systems and does not undergo oxidation during storage, and as a result, by incorporating a thiophosphite compound.

The present invention was achieved by discovering the fact that the photocurability of the composition is improved and the effect is maintained without being oxidized even when the composition is stored for a long period of time.

[Structure of the invention]

The present invention is a photosensitive composition comprising a polyene and a polythiol, which is characterized by containing 0.01 to 20% by weight of a thiophosphite compound represented by the following general formula.

/(S-R,)m p-(S-R2)n \(X-R,)p (R4, R2, and R3 are C5 to C2o alkyl groups, aryl groups, and aralkyl groups, and these have substituents. Toshitehalokene, C4-C2o alkoxy group, alkoxycarbonyl group, acyloxy group, alkanoyl group are also good. X is 0
or -CR4R5-, R4 and R5 are hydrogen, C
4 to '20 alkyl group, aryl group, and aralkyl group. m+n Id An integer from O to B, p indicates an integer from 0 to 2, and m-1-n+p=3. ) The polyene used in the present invention may be any alkene having at least two or more reactive carbon-carbon double bonds per molecule.

Reactive carbon-carbon double bond refers to a bond that reacts with a thiol group under the appropriate conditions described herein.

Further, the polyene preferably used in the present invention has a molecular weight of 200 to 1.
The range is 00,000.

As an example of polyene.

(1) Allyl compounds such as trimethylolpropane triallyl ether, pentaerythritol tetraallyl 1-tyl, triallylisodunurate.

(2) Polyisoprene, polybutadiene, styrene-butadiene rubber, inbutylene-inprene rubber,
W +7 Common elastomers such as chloroprene, styrene-butadiene-acrylonitrile rubber (mainly derivatives of standard diene monomers) (3) Unsaturated polyurethanes by reaction of allyl alcohol with polyisocyanate compounds, polycarboxylic acids,
Examples include, but are not limited to, anionic polymers of unsaturated polyester (4) (meth)acrylic acid allyl ester.

The polythiols that can be used in the present invention have the following general formula (%) () In this formula, l is at least 2, and R is a reactive "carbon-
It is a polyvalent organic residue that does not contain carbon double bonds. R can contain small amounts of cyclic groups or N, S, P heteroatoms, but primarily.

Chain bonds including carbon-carbon, carbon-oxygen, silicon-oxygen bonds are included.

Such polythiols include dimercaptobutane,
Dimercaptohexane, dimercaptodecane, dimercaptoglycerin, thioglycolic acid, α-mercaptopropionic acid or β-mercaptopropionic acid, diol, triol.

Examples include esters with tetraol, pentaol, hexaol, etc.

In addition to the above-mentioned essential components, the photosensitive composition of the present invention contains photopolymerization initiators, photosensitizers, stabilizers such as thermal polymerization inhibitors, compatibility improvers, dyes, pigments, fillers, etc. You can.

By adding a photosensitizer, a highly sensitive photosensitive composition can be obtained. The following primary photosensitizers can be used as such photosensitizers.

Benzoin derivatives such as benzin methyl ether, benzoin isopropyl ether, α, α-dimethoxy α-phenylacetophenone, benzophenone, 2,4
-dichlorobenzophenone, methyl benzoylbenzoate, 4,4/-bis(dimethylamino)benzophenone, benzophenone derivatives such as 4,4/-bis(diethylamino)benzophenone, 2-chlorothioxanthone, 2,4-diinpropyl Thioxanthone derivatives such as thioxanthone, 2-chloroanthrachy/:/,
Anthraquinone derivatives such as 2-methylanthraquinone.

Acridone derivatives such as N-methylacridone and N-butylacridone, α,β-jethoxyacetophenone,
benzyl, fluorenone, xanthone.

Uranyl compounds, halogen compounds, etc.

The thiophosphite compound added in the present invention for the purpose of improving photocurability has the structure of the 9-order general formula (I).

/("-RlL p -(s-R2)n \(X-R, 8 (R11R2J RA is c, ~c2o alkyl group, aryl group, aralkyl group, these are substituted with halogen, C4 ~ c2o may have an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanoyl group, a cyan group, a hydroxyl group, or an amine group.X is O, -
(!R4R5-, R4, R5 are hydrogen, c, ~C
20 alkyl groups, aryl groups, and aralkyl groups are shown.

m and n are integers from 0 to 3, and p is an integer from 0 to 2.
+n+p=5. ) Examples of these compounds include the following: Tributyltrithiophosphite.

Trioctyl trithiophosphite, trilauryl trithiophosphite, triphenyl trithiophosphite, tri(0-tolyl) trithiophosphite, tribenzyl trithiophosphite.

1-'J (2-methoxyethyl> 1-!j thiophosphite, tri(ethoxycarbonylmethyl)trithiophosphite, tri(butoxycarbonylmethyl)
Trithiophosphite, tri(octyloxycarbonylmethyl) trithiophosphite, tri(ro-7toxybutyloxycarbonylmethyl) trithiophosphite, tri(β-ethoxycarbonylethyl) trithiophosphite, tri(β-butoxycarbonylethyl) trithiophosphite), ) lβ-octyloxycarbonylethyl) trithiophosphite, tri(β-6-medoxybutyloxycarbonylethyl) trithiophosphite, tri(β-acetoxyethyl) trithiophosphite, tri(β-cyanoethyl) ) trithiophosphite,
Dilauryl dithiobutyl phosphite, diptyl ethyl thiophosphonate.

Lauryl dibutylthiophosphinate, etc.

The amount of these thiophosphite compounds added is 0.01 to 20% by weight, preferably 0.05 to 1% by weight, based on the photosensitive composition.
If the amount is less than 0.05 to 10% by weight, the effect of improving curability will be small, and if it exceeds 20% by weight, it will be 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.

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

Examples and Comparative Examples\xamethylene diisocyanate) 8.4 g (0.05
mole) totrimethylolpropane diallyl ether 21
．． 4 g (0.1 mol) was charged into a reactor using dioxane as a solvent at a solid content concentration of 20% by weight, and after adding dibutyltin dilaurate as a catalyst at 0.1% by weight based on the solid content, the mixture was heated at a temperature of 50°C. The reaction was allowed to proceed for 1 hour. The obtained reaction product (polyene) will be referred to as prepolymer A.

Add 120 g of 20% solution to this prepolymer (Prepolymer A
, [1,04 mol) topentaerythritol tetrakis (β-thiopropione)) 9.8 g (0°0
2.1 g (0,012 mol) of benzophenone in
After mixing, various thiophosphite compounds were added in an amount of 5% by weight based on the solid content to prepare a photosensitive composition.

This photosensitive composition was applied onto an aluminum plate and dried to obtain a film with a thickness of 0.5 cm. This was irradiated with light from a 1.2 kW high-pressure mercury lamp from a distance of 1 meter under air.

Curing properties were investigated. The number of seconds at which tackiness disappeared was taken as a measure of curability.

The results are shown in Table 1.

Table 1 As is clear from Table 1, the compositions to which a thiophosphite compound was added (Nos. 3 to 5) and the composition to which triphenylphosphine was added (N12) were different from the compositions to which no additive was added (N
The photocurability is significantly improved compared to a j , ). Furthermore, while the composition containing triphenylphosphine (Nα2) lost its improving effect after being stored at 50°C for two weeks, the composition containing a thiophosphite compound (N[13- 5) maintained the same photocurability as the initial state even after storage at 50°C for 2 weeks.

Patent applicant Higashi Shikikai Co., Ltd.

Claims (1)

[Claims] A photosensitive composition consisting of a polyene and a polythiol contains a thiophosphite compound represented by the following general formula.
．． 1. A photosensitive composition comprising 0.01 to 20% by weight. /(S-R4), n P-(S-R2)n \(X-R3)p (R,, R2, R, is a C1-C211 alkyl group, aryl group, aralkyl group, As a substituent, it may have a halogen, a C1-C2o alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanoyl group, a cyan group, a hydroxyl group, or an amine group. X represents O or -CR4R5-, R4, R5 is hydrogen, C1
-C20 alkyl group, aryl group, and aralkyl group. m and n are integers from O to B, p is an integer from 0 to 2,
m10n0p=3. )