JP2001278855A - New sulfonic ester derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sulfonic ester derivative having excellent shelf stability and generating an acid by an action of heat, light, etc., and a new sulfonic ester derivative capable of providing an image forming material having excellent sensitivity, image quality, shelf stability, etc., by using the derivative together with a compound for producing changes in light absorption, hydrophilicity, hydrophobicity, etc., by a reaction with an acid. SOLUTION: This sulfonic ester derivative is represented by general formula (R1SO3CH(R2)R3 (R1 is an alkyl group, an aryl group or a heterocyclic group; R2 and R3 are each independently an alkyl group or an aryl group with the proviso that R2 and R3 are not an aryl group at the same time, R2 and R3 may be bonded to form a ring and at least one of R2 and R3 contains a polymerizable unsaturated group). This polymer is synthesized from a monomer containing the sulfonic ester derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sulfonic acid ester derivative which decomposes under the action of heat, light or the like to generate an acid. The present invention relates to a sulfonic acid ester derivative which is excellent in preservability and efficiently generates an acid by the action of heat, light or the like. The present invention relates to a novel sulfonic acid ester derivative which can provide an image-forming material having excellent sensitivity, image quality, storage stability, etc., when used together with a compound which undergoes a change in absorption, hydrophilicity or hydrophobicity by reaction with an acid. Things.

[0002]

2. Description of the Related Art Sulfonates are widely used as various reactants in organic synthesis. Utilizing the property of decomposing to generate sulfonic acid, it is used as an acid generator in the field of image formation.
As the acid generator, those which generate an acid by the action of heat, light or the like are known, and they are used properly depending on the purpose of use. Among them, a thermal acid generator that generates an acid by heat needs to have both storage stability that does not decompose over time due to heat during storage and activity of an acid generation reaction due to heat, which is insufficient. If there is, the discriminability between the area that has received heat or light and the area that has not received heat is reduced. Investigations have been made to improve the compatibility between this kind of preservability and reaction activity of thermal acid generators, and the outline is described in “Organic Materials for Imaging” (1), edited by Organic Electronics Materials Research Group (Bunshin Publishing).
997), but this point is still extremely insufficient, and further improvement is desired. In recent years, with the advancement of high-power lasers, heat mode image forming media using these lasers have been actively studied. A method of generating an acid by laser irradiation using a high-power laser and forming an image by a reaction between the acid and a dye precursor is disclosed in EP 905,656. In this method, a high-power laser is used. When used, the surface of the image forming medium is partially destroyed by heat (so-called ablation)
And haze increases, causing soiling, etc.,
There are restrictions on raising the reaction temperature. As a result, the compatibility between the reaction activity and the storage stability, that is, the discriminability as a forming material is not sufficient even in a recording method using a laser beam, and the development of an image forming method and a material having practical compatibility has been required. It is still an issue in the field of imaging technology.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a sulfonate derivative which decomposes under the action of heat, light or the like to generate an acid. A second object of the present invention is to provide a sulfonic acid ester derivative which has excellent preservability and efficiently generates an acid by the action of heat, light or the like. A third object of the present invention is to provide an image forming material having excellent sensitivity, image quality, storage stability and the like by using together with a compound which changes light absorption, hydrophilicity / hydrophobicity, etc. by reaction with an acid. An object of the present invention is to provide a novel sulfonic ester derivative.

[0004]

The object of the present invention has been achieved by the following sulfonate derivatives described in 1 to 3. 1. A sulfonic acid ester derivative represented by the following general formula (I).

[0005]

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In the general formula (I), R ¹ represents an alkyl group, an aryl group or a heterocyclic group. R ² and R ³ each independently represent an alkyl group or an aryl group, but neither R ² nor R ³ is an aryl group. R ² and R ³ may combine to form a ring.
However, at least one of R ² and R ³ has a polymerizable unsaturated group.

[0007] 2. A sulfonic acid ester derivative, wherein the sulfonic acid ester derivative represented by the general formula (I) is represented by the following general formula (II).

[0008]

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In the general formula (II), R ¹ has the same meaning as in the general formula (I). X represents an atomic group necessary for forming a ring together with C, and the atomic group constituting X has at least one polymerizable unsaturated group.

[0010] 3. A polymer obtained by polymerizing the sulfonic acid ester derivative represented by the general formula (I) or the general formula (II).

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the general formula (I), R ¹ represents an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, t-
Butyl, n-octyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, [0,1,3]
Bicyclohexyl group, [1,2,2] bicycloheptyl group, [1,2
1,3] bicycloheptyl group, aryl group (phenyl group, naphthyl group, etc.) or heterocyclic group (furyl group, thienyl group, pyrimidinyl group, benzothiazolyl group, etc.). Of these, an alkyl group or an aryl group is preferred, and an aryl group is particularly preferred.
These groups have 1 to 18 carbon atoms, and preferably 1 to 12 carbon atoms, excluding a substituent.

Further, these groups may further have a substituent, and any substituent may be used as long as it can be substituted. A preferable substituent is a halogen atom (Fluorine, chlorine, bromine and iodine),
Alkyl group (specific examples are the same as above, including cycloalkyl group and bicycloalkyl group), alkenyl group (vinyl group, allyl group, prenyl group, geranyl group, oleyl group, 2-cyclopenten-1-yl group, etc.) , Alkynyl group (ethynyl group, propargyl group, trimethylsilylethynyl group, etc.), aryl group (specific examples are as described above), heterocyclic group (specific examples are as described above), cyano group, hydroxyl group, nitro group, carboxyl group , An alkoxy group (methoxy group, ethoxy group, isopropoxy group, t-butoxy group, n-octyloxy group, etc.), an aryloxy group (phenoxy group, naphthoxy group, etc.), a silyloxy group (trimethylsilyloxy group, t-butyldimethyl group) Silyloxy group, etc.), heterocyclic oxy group (pyridyloxy group, 2-tetrahydropyrani Oxy group, etc.), acyloxy group (formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, etc.), carbamoyloxy group (N, N-dimethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N -Di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group, etc., alkoxycarbonyloxy group (methoxycarbonyloxy group, ethoxycarbonyloxy group, t-butoxycarbonyloxy group, n-octylcarbonyloxy group etc),
An aryloxycarbonyloxy group (such as a phenoxycarbonyloxy group),

Furthermore, an amino group (including an anilino group,
Amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group, etc., acylamino group (acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group,
3,4,5-tri-n-octyloxyphenylcarbonylamino group, etc., carbamoylamino group (carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group Etc.), alkoxycarbonylamino group (methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino, n-
Octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino, etc.), aryloxycarbonylamino group (phenoxycarbonylamino group, etc.), sulfamoylamino group (sulfamoylamino group, N,
N-dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group, etc., alkyl and arylsulfonylamino groups (methylsulfonylamino group,
Butylsulfonylamino group, phenylsulfonylamino group, etc.),

Further, mercapto groups, alkylthio groups (methylthio group, ethylthio group, n-hexadecylthio group, etc.), arylthio groups (phenylthio group, etc.), heterocyclic thio groups (2-benzothiazolylthio group, 1-phenyltetrazole- 5-ylthio group, etc.), sulfamoyl group (N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N
-Benzoylsulfamoyl group, N- (N "-phenylcarbamoyl) sulfamoyl group, etc., sulfo group, alkyl and arylsulfinyl group (methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, etc.), alkyl and arylsulfonyl group ( Methylsulfonyl, ethylsulfonyl, phenylsulfonyl, etc.), acyl (acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, etc.), aryloxycarbonyl (phenoxycarbonyl, etc.), alkoxycarbonyl (Methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, n-octadecyloxycarbonyl group, etc.), carbamoyl group (carbamoyl group, N-methylcarbamoyl,
N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group, etc., imide group (N-succinimide group, N-
Phthalimido group), phosphino group (dimethylphosphino group, diphenylphosphino group, etc.), phosphinyl group,
Examples include a phosphinyloxy group, a phosphinylamino group, and a silyl group (such as a trimethylsilyl group, a t-butyldimethylsilyl group, and a phenyldimethylsilyl group). Most preferably, R ¹ is an alkyl group. Specific examples of R ¹ are shown below, but the present invention is not limited thereto.

[0015]

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[0016]

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[0017]

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The substituents R ² and R ³ each independently represent an alkyl group or an aryl group, but R ² and R ³ are not simultaneously aryl groups. Examples of the alkyl group and the aryl group are the same as those described for R ¹ , and may further have a substituent. Preferred substituents are those described for R ¹ . At least one of R ² and R ³ has a polymerizable unsaturated group. As the polymerizable unsaturated group, a vinyl group is preferable. R ² and R ³ may combine to form a ring. Examples of the sulfonic acid ester of the present invention in which R ² and R ³ form a ring include various types, and a preferred form is represented by the general formula (II).

In the general formula (II), R ¹ has the same meaning as in the general formula (I). X represents an atomic group necessary for forming a ring together with C, and has at least one polymerizable unsaturated group. The polymerizable unsaturated group has the same meaning as that described in the description of formula (I). X forms a ring together with C, and the ring size is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring, and particularly preferably a 6-membered ring. X is preferably a non-metallic atomic group, more preferably ^{-C (R 4) (R 5} ) -, - C (=
Y) -, - N (R 6) -, - O -, - 2 -valent group of a plurality of groups selected from S- is an atomic group formed by linear combination,
The plurality of divalent groups may be the same or different. Preferred divalent group ^{is, -C (R 4) (R} 5) - is. Where R
⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a substituent, and preferred examples of the substituent are the same as those described for R ¹ . When a plurality of R ⁴ , R ⁵ or R ⁶ are present in the molecule, they may be the same or different, and any two or more may be combined to form a ring. good. Y is = O, = S, or = N-R
Represents ^6, R ⁶ is -N mentioned above (R ⁶⁾ - which is synonymous with R ⁶ in. Further, among the compounds represented by the general formula (II), more preferred are compounds represented by the following general formula (III).

[0020]

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In the formula, R ¹ has the same meaning as in formula (I).
R ⁷ represents a hydrogen atom or an alkyl group, and the alkyl group may further have a substituent. Specific examples of the alkyl group and the substituent are those described in the specific examples of R ¹ .
R ⁷ is preferably a hydrogen atom or a methyl group. Some of the compounds represented by the general formulas (I), (II) and (III) include isomers such as cis isomers and trans isomers. However, the present invention also includes the case where they are used as a mixture.

Next, polymer compounds derived from these compounds having a polymerizable group will be described. The compounds represented by the general formulas (I) to (III) of the present invention exhibit a greater ability as a functional material by being polymerized. The molecular weight of the polymer of the present invention is preferably in the range of 1,000 to 1,000,000, particularly preferably in the range of 2,000 to 100,000.

The synthesis of the polymer of the present invention can be effected by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, bulk polymerization,
It can be carried out by emulsion polymerization. The method of initiating polymerization includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and the method of initiating the polymerization are described in, for example, T. Tsuruta, “Polymer Synthesis Method” Revised Edition (Nikkan Kogyo Shimbun, 1971), Takatsu Otsu, Masayoshi Kinoshita, “Experimental Method of Polymer Synthesis” Published in 1972,
It is described on pages 124-154.

Among the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferred. Solvents used in the solution polymerization method include, for example, ethyl acetate, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, Various organic solvents such as methylene chloride, chloroform and dichloroethane may be used alone or as a mixture of two or more thereof, or may be used as a mixed solvent with water. The polymerization temperature needs to be set in relation to the molecular weight of the polymer to be produced, the type of initiator, and the like. Polymerization can be performed at various temperatures, but usually the polymerization is carried out in the range of 30 to 100 ° C. In the present invention, it is preferable to carry out the polymerization in a temperature range of 30 to 90C.

Examples of the radical initiator used for the polymerization include 2,2'-azobisisobutyronitrile,
Such as 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-amidinopropane) dihydrochloride, and 4,4'-azobis (4-cyanopentanoic acid) Preferred are azo-based initiators and peroxide-based initiators such as benzoyl peroxide, t-butyl hydroperoxide, and potassium persulfate (for example, redox initiators may be used in combination with sodium bisulfite). In the present invention, the initiator (for example, 2,2'-azobis (2,4-dimethylvaleronitrile)) or 2,2'-azobis (4-methoxy-2,
4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis [2- (3,4,5,6-tetrahydropropane)
Dihydrochloride] and the like are particularly preferred. The amount of the polymerization initiator used can be adjusted according to the polymerizability of the monomer and the required molecular weight of the polymer, but is preferably in the range of 0.01 to 5.0 mol% based on the monomer.

Specific examples of the compound represented by the formula (I), (II) or (III) are shown below, but the present invention is not limited thereto. In addition,
The number of the homopolymer obtained by polymerizing the monomers shown below is represented by adding P- to the number of the monomer (for example, the homopolymer of Exemplified Compound (1) is (P-1), and the same applies to the others). . Depending on the monomer, cis- and tran
Some of the isomers such as the s-isomer exist, and the case where these are polymerized as a mixture is also included in the present invention.

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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The compounds represented by the general formulas (I), (II) and (II)
In synthesizing a polymer from I), in addition to the monomers of the above general formulas, polymerization of at least one or more vinyl monomers capable of forming a copolymer with these monomers may be added to form a copolymer. By controlling the polarity, the glass transition temperature, and the like, depending on the copolymer component, storage stability, color-forming activity, and the like can be controlled. Such vinyl monomers may be used in combination of two or more. Preferred examples include acrylate, methacrylate, acrylamide, styrene, vinyl ether and the like. Specifically, vinyl benzene,
pn-octylvinylbenzene, vinyl-1-naphthalene, methyl acrylate, phenyl acrylate, hydroxymethyl methacrylate, acrylonitrile, N
-Cyclohexylacrylonitrile, N-naphthylacrylonitrile, di-n-butylacrylonitrile and the like, but the present invention is not limited to these. The proportion of these copolymerizable monomers in the copolymer is from 0 to 90 mol%, preferably from 0 to 90 mol%, more preferably from 0 to 50 mol%. The preferred molecular weight and the synthesis method of the copolymer are as described above. Hereinafter, a method for synthesizing the compound of the present invention will be described, but the present invention is not limited thereto. (Synthesis Example 1) Synthesis of Exemplified Compound (1)

[0033]

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The starting compound 1b (mixture of cis- and trans-forms, 100 mmol) was converted to N, N-dimethylacetamide (5
0 ml) and the reactor was cooled to 7 ° C. The starting compound 1a (100 mmol) is added dropwise thereto over 10 minutes,
Thereafter, the reaction was maintained at this temperature for 6 hours. Thereafter, ethyl acetate (200 ml) and water (200 ml) were added and stirred, and then the aqueous layer was separated. The organic layer was further washed three times with 1 mol / l aqueous hydrochloric acid (100 ml), dried over magnesium sulfate and concentrated. The obtained oil is subjected to silica gel column chromatography (eluent: ethyl acetate / hexane =
1/4 → 1/1), and the reaction product 1c was reduced to 61%
In a yield of

Next, the starting compound 1d (50 mmol) was dissolved in pyridine (30 ml) and cooled to 7 ° C. The reaction product 1c (50 mmol) was added thereto, and the mixture was stirred for 8 hours. Thereafter, water (3 ml) was added, and the mixture was stirred for 30 minutes. Then, ethyl acetate (100 ml) and water (200 ml) were added, and the mixture was stirred to separate an aqueous layer. Further, the organic layer was washed with 1 mol / l hydrochloric acid aqueous solution (100
ml), dried over magnesium sulfate and concentrated. The obtained oil is subjected to silica gel column chromatography (eluent: ethyl acetate / hexane = 1/4 → 1 /
Purification was performed in 1) to obtain Exemplified Compound (1) as a mixture of a cis form and a trans form in a yield of 72%. The cis form and the trans form can be separated by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/4 → 1/1). When they were separated and their decomposition temperatures were examined,
The temperature was 192 ° C for the cis form and 184 ° C for the trans form.

(Synthesis Example 2) Synthesis of Exemplified Compound (2)

[0037]

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The starting compound 2a (100 mmol) was dissolved in pyridine (40 ml), and the reactor was cooled to 7 ° C. Thereto, the starting compound 2b (100 mmol) was added dropwise over 10 minutes, and then reacted for 2 hours, and then reacted at room temperature for another 5 hours. Then, after adding water (4 ml) and stirring for 30 minutes, ethyl acetate (150 ml) and water (200 ml) were added and stirred, and the aqueous layer was separated. The organic layer was further washed three times with 1 mol / l aqueous hydrochloric acid (100 ml), dried over magnesium sulfate and concentrated. The obtained oil was purified by silica gel column chromatography (eluent: ethyl acetate / chloroform = 1/8 → 1/1) to obtain a reaction product 2c in a yield of 76%.

Next, the reaction product 2c (50 mmol) was added to N, N
-Dissolved in dimethylacetamide (60 ml) and cooled the reactor to 7 ° C. There, raw material compound 2d (50mmo
l) was added dropwise over 10 minutes, and then reacted at room temperature for 8 hours. After adding ethyl acetate (200 ml) and water (200 ml) and stirring, the aqueous layer was separated. 1mo organic layer
The extract was washed three times with 1 / l aqueous hydrochloric acid (100 ml), dried over magnesium sulfate and concentrated. The obtained oil is subjected to silica gel column chromatography (eluent: ethyl acetate /
Hexane = 1/4 → 1/1) to give Exemplified Compound (2) as a mixture of a cis form and a trans form in a yield of 78%. The decomposition temperature of the trans form of the compound was 189 ° C.

(Synthesis Example 3) Synthesis of Exemplified Compound (3) Same as the synthesis of Exemplified Compound (2) of Synthesis Example 2 except that the starting material compound was changed from 2a to 2,5-xylyl-1-sulfonyl chloride. The compound (3) was synthesized by the above reaction to obtain a mixture of a cis form and a trans form. The decomposition temperature of the mixture was 181 ° C.

(Synthesis Example 4) Synthesis of Exemplified Compound (22) Synthesis Example 2 except that the starting material 2a was changed to p-tolylsulfonyl chloride and the starting material 2d was changed to acryl chloride.
Synthesized in the same reaction as the exemplified compound (2) of
Obtained as a mixture of rans bodies. The decomposition temperature of cis isomer is 182
° C, the decomposition temperature of the trans form was 173 ° C.

(Synthesis Example 5) Synthesis of Exemplified Compound (13) Except that the starting material 2a was changed to p-tolylsulfonyl chloride and the starting material 2b was changed to 4- [2- (4-hydroxybutylcyclohexyl] propyl) cyclohexanol The compound (13) was obtained as a mixture of a cis-form and a trans-form by the same reaction as in the synthesis of the exemplified compound (2) of Synthesis Example 2. The decomposition temperature of the mixture was measured, but no clean decomposition peak was obtained.

Synthesis Example 6 Synthesis of Polymer (P-1) Polymer (1) (50 mmol) was dissolved in toluene (22 ml) and heated to 40 ° C. under a nitrogen atmosphere. There
A solution of 2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (0.125 g) in methyl ethyl ketone (3 ml) was added and reacted for 2 hours, followed by 2,2′-azobis (4-methoxy-methyl). A solution of 2,4-dimethylvaleronitrile) (0.125 g) in methyl ethyl ketone (3 ml) was added. After reacting for 2 hours, the reaction solution was poured into hexane (1200 ml), and the precipitate was collected by filtration and dried to obtain 89% of polymer (P-1).
% Yield. The weight average molecular weight was 85,000 and the decomposition temperature was 172 ° C.

(Synthesis Example 7) Synthesis of Polymer (P-2) Polymer (P-2) was synthesized by the same reaction as synthesis of polymer (P-1) using Exemplified Compound (2). The weight average molecular weight was 120,000 and the decomposition temperature was 187 ° C.

(Synthesis Example 8) Synthesis of polymer (P-3) Using the exemplified compound (3), a polymer (P-3) was synthesized by the same reaction as in the synthesis of the polymer (P-1). The weight average molecular weight was 100,000, and the decomposition temperature was 174 ° C.

(Synthesis Example 9) Synthesis of polymer (P-22) Using the exemplified compound (22), a polymer (P-22) was synthesized by the same reaction as in the synthesis of the polymer (P-1). The mass average molecular weight was 175,000 and the decomposition temperature was 165 ° C.

[0047]

The following examples illustrate the usefulness of the compounds of the present invention in more detail, but the present invention is not limited thereto. (Example 1) In Example 1, the compound of the present invention is compared with a comparative compound having a similar structure to the compound of the present invention in terms of the thermal decomposition temperature. As the compounds of the present invention, the thermal decomposition temperatures of the exemplified compounds (1) to (8) shown in the above Synthesis Examples are all 16 as described in the Synthesis Examples.
Between 5 and 192 ° C. R-1 and R-2 were synthesized as known comparative compounds having similar structures. These are those in which a polymerizable group is attached to a sulfonic acid site (a portion corresponding to R ¹ in the general formula I) of a sulfonic acid ester, R-1 is a monomer, and R-2 is a polymer obtained by polymerizing the monomer. is there. These decomposition temperatures are 133 ° C,
The temperature was 112 ° C, and the decomposition temperature was low and unstable. The above-mentioned compounds of the present invention have a decomposition temperature of at least 32 ° C. and a maximum of 8
The temperature was as high as 0 ° C. (decomposition temperature is described in the column of Synthesis Example), and it was stable. As described above, a very useful design in which the decomposition temperature can be increased despite the similar structures can be found.

[0048]

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Example 2 A polymer represented by Formula 4 was synthesized by copolymerizing the monomer of the present invention and the monomer of Comparative Example. In the formula, A represents an acid generator;
The numbers 30 and 30 represent the molar ratio of each monomer. The polymer was synthesized by mixing monomers constituting the polymer at a molar ratio of 70:30 in toluene and performing radical polymerization.
The polymerization reaction was carried out in the same manner as in the synthesis example of the homopolymer (P-1).

[0050]

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Table 1 shows a list of the synthesized polymers. These polymers and the following IR dye was mixed solution was dissolved in chloroform, the acid generator moiety 5 mmol / m ^2, chloroform lysates as IR dye is 0.15 mmol / m ^2,
It was applied on a polyethylene terephthalate film having a thickness of 175 μm. The image recording characteristics of heat or light sensitivity (heat mode light) of the image forming material thus obtained were measured by a laser light irradiation test. Laser exposure, Spectr
a Diode Labs No.SDL-2430 laser oscillator (wavelength range:
(800 to 830 nm) were combined to obtain an output of 140 mW to obtain an image writing laser beam. Using this laser, the beam diameter was set to 20 μm, and the irradiation energy density of the laser light on the sample was set to 4.5 mJ / mm ² . After scanning exposure was performed from the protective layer side of the image forming material under the laser exposure conditions, thermal development was performed at 120 ° C. for 30 seconds, and the infrared absorption change of the polymer ester was determined to evaluate the reactivity. A sample of the image forming material was subjected to a humidity-free condition (expressed as dry) at 45 ° C and a humidity of 70 ° C at 45 ° C.
%, Each was allowed to stand for 7 days, and then the disappearance of the polymer ester was measured to evaluate the storage stability of the sample. Evaluation of the storage stability and the reactivity
R absorption was measured, and the IR (1640)
nm) absorption of ester (1640n
m) (Tables 2 and 3). The extinction rate of IR absorption by laser light of the image forming material immediately after preparation is as follows.
The smaller the value of the activity of the acid generation reaction caused by light irradiation in the heat mode, the higher the activity. It is. As is clear from the results in Tables 2 and 3, all of the compounds using the monomer of the present invention have good reactivity and storage stability, and the compound of the present invention is used as an image forming material triggered by acid generation. The utility was clear.

[0052]

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[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

Industrial Applicability The sulfonic acid ester of the present invention, which generates an acid by the action of light or heat, and its polymer are more stable during storage than conventional acid generators, and can be exposed to heat or heat mode light. It reacts sensitively and has high discrimination between the light irradiation area and the non-irradiation area. Therefore, there is a wide application as a forming means used together with a substance which causes a change in physical properties by an acid, particularly a change in color or hydrophobicity, including application to a high quality image forming material.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AB16 AC08 AD03 BE00 4H006 AA01 AB80 AB81 AB99 4J100 AL08P AP01P BA02P BA03P BA04P BA05P BA20P BA29P BA30P BA31P BA34P BA40P BA41P BA52P BA58P BA59P BA77P BB01P04 BC03P03 BC BB01P04 BC03P03BC BC49P BC53P BC66P BC73P BC79P BC83P CA01 JA32

Claims (3)

[Claims] 1. A sulfonic acid ester derivative represented by the following general formula (I). [Formula 1] (In the formula, R ¹ represents an alkyl group, an aryl group or a heterocyclic group .R ² and R ³ are each independently an alkyl group or aryl group, R ² and R ³ are both aryl group R ² and R ³ may combine to form a ring, provided that at least one of R ² and R ³ has a polymerizable unsaturated group.) 2. The sulfonic acid ester derivative according to claim 1, wherein the sulfonic acid ester derivative represented by the general formula (I) is represented by the following general formula (II). Embedded image (Wherein R ¹ has the same meaning as in general formula I. X represents an atomic group necessary for forming a ring together with C, and the atomic group constituting X has at least one polymerizable unsaturated group. .) 3. A polymer obtained by polymerizing a sulfonic acid ester derivative represented by the general formula (I) according to claim 1 or the general formula (II) according to claim 2.